US20050160663A1 - Cleaner burning diesel fuel - Google Patents
Cleaner burning diesel fuel Download PDFInfo
- Publication number
- US20050160663A1 US20050160663A1 US11/038,286 US3828605A US2005160663A1 US 20050160663 A1 US20050160663 A1 US 20050160663A1 US 3828605 A US3828605 A US 3828605A US 2005160663 A1 US2005160663 A1 US 2005160663A1
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- diesel fuel
- fuel
- platinum
- biodiesel
- cerium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
- F01N3/0232—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 removing incombustible material from a particle filter, e.g. ash
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- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
- F01N3/106—Auxiliary oxidation catalysts
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- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
- F02D19/0649—Liquid fuels having different boiling temperatures, volatilities, densities, viscosities, cetane or octane numbers
- F02D19/0652—Biofuels, e.g. plant oils
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- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/08—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed simultaneously using pluralities of fuels
- F02D19/082—Premixed fuels, i.e. emulsions or blends
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- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
- F02M25/14—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding anti-knock agents, not provided for in subgroups F02M25/022 - F02M25/10
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/1241—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof metal carbonyls
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/14—Organic compounds
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- C10L1/1814—Chelates
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1888—Carboxylic acids; metal salts thereof tall oil
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- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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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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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
- Y02T50/678—Aviation using fuels of non-fossil origin
Definitions
- the invention provides an improved diesel fuel based on a blend of biodiesel and a low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst (FBC).
- FBC fuel borne catalyst
- the invention provides an improved diesel fuel based on a blend of biodiesel and low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst.
- the invention provides an improved diesel fuel based on a blend of biodiesel and low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst (FBC).
- FBC fuel borne catalyst
- a low aromatic (LA) content, ultralow sulfur diesel (ULSD) fuel As a principal component of the fuel blends of the invention, there is provided a low aromatic (LA) content, ultralow sulfur diesel (ULSD) fuel.
- low aromatic content as used herein means that this component of the fuel will have an aromatic content in volume percent of less than 10%, and preferably of from 1 to 8%, particularly in the range of from 2 to 5%.
- the table below shows typical analyses of a No. 2 diesel and low aromatic ultralow sulfur diesel fuels LA ULSD, in addition to a preferred formulation according to the invention (LA ULSD with FBC and 20% Bio-Diesel). Equivalents which have the same essential function and those varying compositionally by up to 50%, preferably by less than 20%, e.g., no more than 10%, can also be employed.
- Biodiesel will comprise a minor proportion of the fuel blend, typically from about 1 to 35%, e.g., on the order of 15 to 25%. Blends will typically contain about 20% biodiesel, wherein this biologically-derived fuel component will be comprised of a “mono-alkyl ester-based oxygenated fuel”, i.e., fatty acid esters, preferably from fatty acids derived from triglycerides such as soybean oil, Canola oil and/or tallow.
- a “mono-alkyl ester-based oxygenated fuel” i.e., fatty acid esters, preferably from fatty acids derived from triglycerides such as soybean oil, Canola oil and/or tallow.
- fatty acid ester(s) is intended to include any compound wherein the alcohol portion is easily removed, including polyols and substituted alcohols, etc., but are preferably esters of volatile alcohols, e.g., the C 1 -C 4 alcohols (preferably methyl), 2-methoxy ethyl and benzyl esters of fatty acids containing about eight or more (e.g., 8 to 22) carbon atoms, and mixtures of such esters. Volatile alcohols are highly desirable. Methyl esters are the most highly preferred ester reactants. Suitable ester reactants can be prepared by the reaction of diazoalkanes and fatty acids, or derived by alcoholysis from the fatty acids naturally occurring in fats and oils.
- Suitable fatty acid esters can be derived from synthetic or natural, saturated or unsaturated fatty acids and include positional and geometrical isomers.
- Suitable preferred saturated fatty acids include caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, isomyristic, isomargaric, myristic, caprylic, and anteisoarachadic.
- Suitable preferred unsaturated fatty acids include myristoleic, palmitoleic, ricinoleic, linoleic, oleic, elaidic, linolenic, eleasteric, arachidonic, erucic, and erythrogenic acids.
- fatty acids derived from soybean oil, palm oil, safflower oil, rapeseed oil, Canola (low ericic acid), and corn oil are especially preferred for use herein.
- the fatty acids can be used “as is,” and/or after hydrogenation, and/for isomerization, and/for purification.
- rapeseed provides a good source for C 22 fatty acids
- C 16 -C 18 fatty acids can be provided by tallow, soybean oil, or cottonseed oil
- shorter chain fatty acids can be provided by coconut, palm kernel, or babassu oils.
- Lard, olive oil, peanut oil, sesame seed oil, and sunflower seed oil, are other natural sources of fatty acids.
- Preferred esters comprised in the biodiesel are lower alkyl esters, e.g., methyl, ethyl, propyl and butyl, particularly methyl esters of soybean and or tallow fatty acids.
- biodiesel B100
- biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, for use in compression-ignition (diesel) engines. This specification is for pure (100%) biodiesel prior to use or blending with diesel fuel.
- One product of this type is available under the trademark BioDiesel by Members of the National BioDiesel Board and is identified as “Methyl Soyate, Rapeseed Methyl Ester (RME), Methyl Tallowate”.
- the manufacturer also refers to the fuel as “a mono-alkyl ester-based oxygenated fuel, a fuel made from vegetable oil or animal fats.” It is said to contain 11% oxygen by weight. They describe the product as Methyl esters from lipid sources, CAS Number 67784-80-9.
- the fuel borne catalyst will comprise fuel-soluble platinum and/or cerium and/or iron.
- the cerium and/or iron are typically employed at concentrations of from 2 to 25 ppm and the platinum from 0.05 to 2 ppm, with preferred levels of cerium or iron being from 2 to 10 ppm, e.g., 3-8 ppm, and the platinum being employed at a level of from 0.1 to 0.5 ppm, e.g., 0.15 ppm.
- a preferred ratio of cerium and/or iron to platinum is from 75:1 to 10:1.
- the LA ULSD component will typically be employed at a volume ratio to the fatty acid esters of from about 2:1 to about 5:1, e.g., about 4:1.
- the full range of blends extends from 50:1 to 1:50 with some benefit.
- the LA ULSD fuel component of the blend preferably contains 50-1500 ppm detergent, up to about 500 ppm lubricity additive and 0.1-1 ppm platinum COD and 5-20 ppm cerium oleate or octoate. It is an advantage of the invention that the fatty acid esters add lubricity to the LA ULSD and decrease the need for independent lubricity additives.
- the catalyzed blend of the invention is effective in lowering regulated emission pollutants, among which are NO x , particulates, hydrocarbons and carbon monoxide.
- the fuel will lower NO x and particulates at the same time, an unusual combination.
- Preferred blends will be effective to achieve at least a 4% or more reduction in NO x and a particulate reduction of at least 25% as compared to a baseline of No. 2 Diesel fuel. More preferred levels will be from 5 to 25% NO x reduction and from 20 to 60% particulate reduction.
- Higher reductions of particulates can be achieved by using the fuel in an engine equipped with a diesel particulate filter or diesel oxidation catalyst. These reductions are preferably obtained while reducing or not increasing NO 2 emissions.
- a preferred detergent which can be employed, comprises polyolefin amide alkyleneamine (about 65-80%) and the remainder petroleum distillate. Equivalents which have the same essential function can also be employed.
- One preferred form is available from Texaco as TFA-4690-C, at concentrations of from about 50 to 300 ppm, more narrowly 75-150, e.g., about 100 ppm, for which they provide the following analysis: Properties Method Typical Density @ 15° C. D4052 0.91-0.94 Nitrogen Content, wt. % D5291 2.3-2.4 Flash, ° C., minimum D93 62 TBN, mgKOH/g D2896 50-60 Kinematic Viscosity, D445 600-850 cSt at 40° C.
- a preferred lubricity additive which can be employed, comprises tall oil fatty acids, available commercially as a mixture of fatty acids including oleic, linoleic and the like. Equivalents which have the same essential function can also be employed.
- One preferred form is available from Texaco as TFA-4769, at concentrations of from about 25 to 500 ppm, e.g., about 150-250 ppm, for which they provide the following analysis: Properties Method Typical Specific Gravity, D1298 0.91 60/60° F. Pounds/Gallon, 60° F. Calculated 7.54 Flash, ° F., minimum D93 142 Kinematic Viscosity, D445 17.85 cSt at 40° C.
- cerium III acetylacetonate cerium III napthenate
- cerium octoate cerium oleate and other soaps such as stearate, neodecanoate, and octoate (2-ethylhexoate).
- the cerium is preferred at concentrations of 2 to 15 ppm cerium w/v of fuel.
- the cerium is supplied as cerium hydroxy oleate propionate complex (40% cerium by weight). Preferred levels are toward the lower end of this range.
- iron compounds include ferrocene, ferric and ferrous acetyl-acetonates, iron soaps like octoate and stearate (commercially available as Fe(III) compounds, usually), iron pentacarbonyl Fe(CO).sub.5, iron napthenate, and iron tallate.
- platinum group metal compositions e.g., 1,5-cyclooctadiene platinum diphenyl (platinum COD), described in U.S. Pat. No. 4,891,050 to Bowers, et al., U.S. Pat. No. 5,034,020 to Epperly, et al., and U.S. Pat. No. 5,266,093 to Peter-Hoblyn, et al., can be employed as the platinum source.
- platinum COD 1,5-cyclooctadiene platinum diphenyl
- platinum group metal catalyst compositions include commercially-available or easily-synthesized platinum group metal acetylacetonates, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes, e.g., tetramine platinum oleate.
- the platinum is preferred at concentrations of 0.1-2.0 ppm platinum w/v (mg per liter) of fuel, e.g., up to about 1.0 ppm. Preferred levels are toward the lower end of this range, e.g., 0.15-0.5 ppm.
- Platinum COD is the preferred form of platinum for addition to the fuel.
- the cerium or iron are typically employed at concentrations to provide from 2 to 25 ppm of the metal and the platinum from 0.05 to 2 ppm, with preferred levels of cerium or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the platinum being employed at a level of from 0.1 to 0.5 ppm, e.g., 0.15 ppm.
- a preferred ratio of cerium and/or iron to platinum is from 75:1 to 10:1.
- retarding engine timing e.g., from 2 to 6°
- retarding engine timing can further reduce NO x and the use of a diesel particulate filter and/or diesel oxidation catalyst can provide further reductions in carbon monoxide, unburned hydrocarbons and particulates.
- the low-emissions fuel according to the invention can be employed as an emulsion with water, wherein an oil phase is emulsified with water, the water comprising from 1 to 30% water based on the weight of the aviation kerosene.
- the emulsion will be predominantly of the water-in-oil type and will preferably contain surfactants, lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above.
- surfactants lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above.
- suitable emulsion forms and additives is found in U.S. Pat. No. 5,743,922.
- An emulsion of the water-in-oil type typically provides about 1% NO x reduction for each 1% water added. The combination of technologies will provide emissions reductions greater than either alone.
- the platinum/cerium fuel borne catalyst or other catalyst is preferred but optional. If desired, the combination of a blend of fatty acid esters and aviation kerosene can be employed to good effect without the fuel borne catalyst.
- the fuel thus formed in any of the embodiments above, can be used with timing changes, EGR, oxidation catalysts or particulate filters for enhanced emissions control.
- diesel particulate filter is meant to refer to those devices known in the art as exhaust gas filters that reduce particulate emissions by trapping a portion of the particulates within a complex internal structure. They must be regenerated or replaced as deposits will accumulate.
- diesel oxidation catalyst is meant to refer to those devices known in the art as exhaust gas treatment catalysts that reduce particulate, hydrocarbon and carbon monoxide emissions by causing contact with catalyzed surfaces in lieu of trapping particulates as done in the diesel particulate filters.
- Retarding engine timing e.g., by from about 2 to about 6°
- Retarding engine timing is a known procedure for reducing NO x , unfortunately it will by itself cause pollutant generation due to poor combustion. This tradeoff has been troubling the art since emissions control became important. It is an advantage of the invention, that both reduced NO x and other pollutants can be achieved by employing the fuel of the invention in combination with one or more of the above techniques and/or exhaust gas recirculation wherein a portion of the exhaust gas is intermixed with combustion air.
- an FBC is provided, such as described in U.S. Pat. No. 6,003,303 and the references cited therein.
- the invention has particular utility in the operation of fleet vehicles, which are brought to a central location for refueling at regular intervals, e.g., daily.
- the concentration of FBC catalyst metal in fuel is desirably maintained between 4 and 10 ppm in this exemplary setting.
- Cleaner burning biodiesel fuel blends used with the Platinum Plus® fuel borne catalyst (FBC) (added at 0.15 ppm Pt as Pt COD) and a lightly catalyzed (3-5 grams Pt) diesel oxidation catalyst (DOC) produced emission reductions of 51 percent particulates (PM) and 9 percent NOx versus baseline emissions from standard No. 2D fuel.
- FBC Platinum Plus® fuel borne catalyst
- DOC diesel oxidation catalyst
Abstract
An improved diesel fuel based on a blend of biodiesel and ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst (FBC). The catalyst will preferably comprise platinum and/or cerium and/or iron, and the ultra-low sulfur diesel fuel will preferably contain less than 10% aromatics. The biodiesel is typically employed in an amount of about 20% of the blend.
Description
- This is a continuation in part of and claims priority to pending U.S. patent application Ser. No. 10/357,027 filed 3 Feb. 3, which claims priority to PCT/US01/24061, which claims priority to U.S. Provisional Patent Application 60/222,252, filed 1 Aug. 2000.
- The invention provides an improved diesel fuel based on a blend of biodiesel and a low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst (FBC).
- In U.S. patent application Ser. No. 10/290,798, there is described a Low Emissions Diesel Fuel, which includes jet A and an FBC.
- In U.S. patent application Ser. No. 10/357,027, there is described a Low Emissions Diesel Fuel, which includes an emulsion of jet A and an FBC.
- In U.S. patent application Ser. No. 10/401,367, there is described a Low Emissions Diesel Fuel, which includes jet A, biodiesel and an FBC.
- These fuels are indeed effective, but there is a continuing need for additional diesel fuels to provide yet further reductions in pollutant generation, especially NOx and particulate emissions.
- It is an objective of the invention to provide an improved diesel fuel to reduce emissions of unburned hydrocarbons, carbon monoxide, particulates and NOx.
- It is another objective of the invention to provide a fuel employing renewable source materials having a desirable balance of hydrogen to carbon, which can decrease carbon dioxide emissions by this means and fuel economy as the emission of noxious pollutants are also controlled.
- These and other objects are accomplished by the invention which provides an improved diesel fuel based on a blend of biodiesel and low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst.
- Several preferred aspects of the invention will be described below.
- The invention provides an improved diesel fuel based on a blend of biodiesel and low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing fuel borne catalyst (FBC).
- As a principal component of the fuel blends of the invention, there is provided a low aromatic (LA) content, ultralow sulfur diesel (ULSD) fuel. The term low aromatic content as used herein means that this component of the fuel will have an aromatic content in volume percent of less than 10%, and preferably of from 1 to 8%, particularly in the range of from 2 to 5%. The table below shows typical analyses of a No. 2 diesel and low aromatic ultralow sulfur diesel fuels LA ULSD, in addition to a preferred formulation according to the invention (LA ULSD with FBC and 20% Bio-Diesel). Equivalents which have the same essential function and those varying compositionally by up to 50%, preferably by less than 20%, e.g., no more than 10%, can also be employed.
Typical Preferred Low LA ULSD Typical Aromatic (LA) with FBC and Fuel No. 2 Diesel ULSD 20% Bio-Diesel API Gravity 36.36 35-40 35-40 Sulfur, wt % 0.0323 <0.0015 <0.0015 Cetane Number 47.7 >47 >50 Carbon, wt % 86.84 <87 <85 Hydrogen, wt % 13.16 >13 >13 Aromatics, vol % 29.9 <10 ND Olefins, vol % 0.5 ND ND Saturates, vol % 69.6 ND ND Viscosity at 40 C. (cs) 2.3 <10, e.g. 2-3 ND Flash Point, ° F. 157.4 >180 ND IBP, ° F. 351.1 420-430 430 5%, ° F. 393.3 ND 449 10%, ° F. 414.0 >440 459 20%, ° F. 439.0 ND 478 30%, ° F. 459.5 ND 493 40%, ° F. 477.9 ND 509 50%, ° F. 494.6 >490 526 60%, ° F. 511.3 ND 544 70%, ° F. 529.0 ND 567 80%, ° F. 550.4 ND 592 90%, ° F. 580.3 >560 618 95%, ° F. 606.7 ND 633 EP, ° F. 641.7 <640 643 - The other principal ingredient of the low-emissions diesel fuel of the invention is what is referred to in the art as “biodiesel”. Biodiesel will comprise a minor proportion of the fuel blend, typically from about 1 to 35%, e.g., on the order of 15 to 25%. Blends will typically contain about 20% biodiesel, wherein this biologically-derived fuel component will be comprised of a “mono-alkyl ester-based oxygenated fuel”, i.e., fatty acid esters, preferably from fatty acids derived from triglycerides such as soybean oil, Canola oil and/or tallow. As used herein, the term “fatty acid ester(s)” is intended to include any compound wherein the alcohol portion is easily removed, including polyols and substituted alcohols, etc., but are preferably esters of volatile alcohols, e.g., the C1-C4 alcohols (preferably methyl), 2-methoxy ethyl and benzyl esters of fatty acids containing about eight or more (e.g., 8 to 22) carbon atoms, and mixtures of such esters. Volatile alcohols are highly desirable. Methyl esters are the most highly preferred ester reactants. Suitable ester reactants can be prepared by the reaction of diazoalkanes and fatty acids, or derived by alcoholysis from the fatty acids naturally occurring in fats and oils.
- Suitable fatty acid esters can be derived from synthetic or natural, saturated or unsaturated fatty acids and include positional and geometrical isomers. Suitable preferred saturated fatty acids include caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, isomyristic, isomargaric, myristic, caprylic, and anteisoarachadic. Suitable preferred unsaturated fatty acids include myristoleic, palmitoleic, ricinoleic, linoleic, oleic, elaidic, linolenic, eleasteric, arachidonic, erucic, and erythrogenic acids. Mixtures of fatty acids derived from soybean oil, palm oil, safflower oil, rapeseed oil, Canola (low ericic acid), and corn oil are especially preferred for use herein. The fatty acids can be used “as is,” and/or after hydrogenation, and/for isomerization, and/for purification. For example, rapeseed provides a good source for C22 fatty acids; C16-C18 fatty acids can be provided by tallow, soybean oil, or cottonseed oil; and shorter chain fatty acids can be provided by coconut, palm kernel, or babassu oils. Lard, olive oil, peanut oil, sesame seed oil, and sunflower seed oil, are other natural sources of fatty acids.
- Preferred esters comprised in the biodiesel are lower alkyl esters, e.g., methyl, ethyl, propyl and butyl, particularly methyl esters of soybean and or tallow fatty acids. The following is the specification for biodiesel (B100) set by the National Biodiesel Board, December 2001, which is also adopted for the purpose of clarity and definition for the present invention. Thus, biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, for use in compression-ignition (diesel) engines. This specification is for pure (100%) biodiesel prior to use or blending with diesel fuel. A considerable amount of experience exists in the US with a 20% blend of biodiesel with 80% diesel fuel (B20). Although biodiesel (B100) can be used, blends of over 20% biodiesel with diesel fuel should be evaluated on a case-by-case basis until further experience is available. Equivalents which have the same essential function and those varying compositionally by up to 25%, preferably by less than 10%, can also be employed. In some cases, as little as 2% biodiesel may be used with a blend of 98% diesel fuel of distillate origin.
Property ASTM Method Limits Units Flash Point D93 130 min. Degrees C. Water & Sediment D2709 0.050 max. % vol. Kinematic Viscosity, D445 1.9-6.0 mm2/sec. 40 C. Sulfated Ash D874 0.020 max. % mass Sulfur D5453 15 max. ppm S 15 Grade 500 max. S 500 Grade Copper Strip Corrosion D130 No. 3 max. Cetane D613 47 min. Cloud Point D2500 Pref. −2° C. or Degrees C. Report Carbon Residue D45301 0.050 max. % mass 100% sample Acid Number D664 0.80 max. mg KOH/gm Free Glycerin D6584 0.020 max. % mass Total Glycerin D6584 0.240 max. % mass Phosphorus Content D 4951 0.001 max. % mass Distillation Temp, D 1160 360 max. Degrees C. Atmospheric Equivalent Temperature, 90% Recovered
1To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller and manufacturer.
- One product of this type is available under the trademark BioDiesel by Members of the National BioDiesel Board and is identified as “Methyl Soyate, Rapeseed Methyl Ester (RME), Methyl Tallowate”. The manufacturer also refers to the fuel as “a mono-alkyl ester-based oxygenated fuel, a fuel made from vegetable oil or animal fats.” It is said to contain 11% oxygen by weight. They describe the product as Methyl esters from lipid sources, CAS Number 67784-80-9.
- The fuel borne catalyst (FBC) will comprise fuel-soluble platinum and/or cerium and/or iron. The cerium and/or iron are typically employed at concentrations of from 2 to 25 ppm and the platinum from 0.05 to 2 ppm, with preferred levels of cerium or iron being from 2 to 10 ppm, e.g., 3-8 ppm, and the platinum being employed at a level of from 0.1 to 0.5 ppm, e.g., 0.15 ppm. A preferred ratio of cerium and/or iron to platinum is from 75:1 to 10:1. The LA ULSD component will typically be employed at a volume ratio to the fatty acid esters of from about 2:1 to about 5:1, e.g., about 4:1. The full range of blends extends from 50:1 to 1:50 with some benefit. The LA ULSD fuel component of the blend preferably contains 50-1500 ppm detergent, up to about 500 ppm lubricity additive and 0.1-1 ppm platinum COD and 5-20 ppm cerium oleate or octoate. It is an advantage of the invention that the fatty acid esters add lubricity to the LA ULSD and decrease the need for independent lubricity additives.
- The catalyzed blend of the invention is effective in lowering regulated emission pollutants, among which are NOx, particulates, hydrocarbons and carbon monoxide. Preferably the fuel will lower NOx and particulates at the same time, an unusual combination. Preferred blends will be effective to achieve at least a 4% or more reduction in NOx and a particulate reduction of at least 25% as compared to a baseline of No. 2 Diesel fuel. More preferred levels will be from 5 to 25% NOx reduction and from 20 to 60% particulate reduction. Higher reductions of particulates can be achieved by using the fuel in an engine equipped with a diesel particulate filter or diesel oxidation catalyst. These reductions are preferably obtained while reducing or not increasing NO2 emissions.
- A preferred detergent, which can be employed, comprises polyolefin amide alkyleneamine (about 65-80%) and the remainder petroleum distillate. Equivalents which have the same essential function can also be employed. One preferred form is available from Texaco as TFA-4690-C, at concentrations of from about 50 to 300 ppm, more narrowly 75-150, e.g., about 100 ppm, for which they provide the following analysis:
Properties Method Typical Density @ 15° C. D4052 0.91-0.94 Nitrogen Content, wt. % D5291 2.3-2.4 Flash, ° C., minimum D93 62 TBN, mgKOH/g D2896 50-60 Kinematic Viscosity, D445 600-850 cSt at 40° C. - A preferred lubricity additive, which can be employed, comprises tall oil fatty acids, available commercially as a mixture of fatty acids including oleic, linoleic and the like. Equivalents which have the same essential function can also be employed. One preferred form is available from Texaco as TFA-4769, at concentrations of from about 25 to 500 ppm, e.g., about 150-250 ppm, for which they provide the following analysis:
Properties Method Typical Specific Gravity, D1298 0.91 60/60° F. Pounds/Gallon, 60° F. Calculated 7.54 Flash, ° F., minimum D93 142 Kinematic Viscosity, D445 17.85 cSt at 40° C. - Among the specific cerium compounds are: cerium III acetylacetonate, cerium III napthenate, and cerium octoate, cerium oleate and other soaps such as stearate, neodecanoate, and octoate (2-ethylhexoate). Many of the 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 cerium is preferred at concentrations of 2 to 15 ppm cerium w/v of fuel. Preferably, the cerium is supplied as cerium hydroxy oleate propionate complex (40% cerium by weight). Preferred levels are toward the lower end of this range.
- Among the specific iron compounds are: ferrocene, ferric and ferrous acetyl-acetonates, iron soaps like octoate and stearate (commercially available as Fe(III) compounds, usually), iron pentacarbonyl Fe(CO).sub.5, iron napthenate, and iron tallate.
- Any of the platinum group metal compositions, e.g., 1,5-cyclooctadiene platinum diphenyl (platinum COD), described in U.S. Pat. No. 4,891,050 to Bowers, et al., U.S. Pat. No. 5,034,020 to Epperly, et al., and U.S. Pat. No. 5,266,093 to Peter-Hoblyn, et al., can be employed as the platinum source. Other suitable platinum group metal catalyst compositions include commercially-available or easily-synthesized platinum group metal acetylacetonates, platinum group metal dibenzylidene acetonates, and fatty acid soaps of tetramine platinum metal complexes, e.g., tetramine platinum oleate. The platinum is preferred at concentrations of 0.1-2.0 ppm platinum w/v (mg per liter) of fuel, e.g., up to about 1.0 ppm. Preferred levels are toward the lower end of this range, e.g., 0.15-0.5 ppm. Platinum COD is the preferred form of platinum for addition to the fuel. The cerium or iron are typically employed at concentrations to provide from 2 to 25 ppm of the metal and the platinum from 0.05 to 2 ppm, with preferred levels of cerium or iron being from 5 to 10 ppm, e.g., 7.5 ppm, and the platinum being employed at a level of from 0.1 to 0.5 ppm, e.g., 0.15 ppm. A preferred ratio of cerium and/or iron to platinum is from 75:1 to 10:1.
- In addition to utilizing the low-emissions fuel according to the invention, retarding engine timing, e.g., from 2 to 6°, can further reduce NOx and the use of a diesel particulate filter and/or diesel oxidation catalyst can provide further reductions in carbon monoxide, unburned hydrocarbons and particulates.
- The low-emissions fuel according to the invention can be employed as an emulsion with water, wherein an oil phase is emulsified with water, the water comprising from 1 to 30% water based on the weight of the aviation kerosene. In the preferred forms, the emulsion will be predominantly of the water-in-oil type and will preferably contain surfactants, lubricity additives and/or corrosion inhibitors in addition to the other components mentioned above. A discussion of suitable emulsion forms and additives is found in U.S. Pat. No. 5,743,922. An emulsion of the water-in-oil type typically provides about 1% NOx reduction for each 1% water added. The combination of technologies will provide emissions reductions greater than either alone. The platinum/cerium fuel borne catalyst or other catalyst is preferred but optional. If desired, the combination of a blend of fatty acid esters and aviation kerosene can be employed to good effect without the fuel borne catalyst. The fuel thus formed in any of the embodiments above, can be used with timing changes, EGR, oxidation catalysts or particulate filters for enhanced emissions control.
- The term “diesel particulate filter” is meant to refer to those devices known in the art as exhaust gas filters that reduce particulate emissions by trapping a portion of the particulates within a complex internal structure. They must be regenerated or replaced as deposits will accumulate. The fuel borne catalyst described above, when used with the base fuel as also described—forming the fuel of the invention—enables very reduced emissions with enhanced filter operation.
- The term “diesel oxidation catalyst” is meant to refer to those devices known in the art as exhaust gas treatment catalysts that reduce particulate, hydrocarbon and carbon monoxide emissions by causing contact with catalyzed surfaces in lieu of trapping particulates as done in the diesel particulate filters. The fuel borne catalyst described above, when used with the base fuel as also described—forming the fuel of the invention—enables very reduced emissions with enhanced oxidation catalyst operation.
- Retarding engine timing, e.g., by from about 2 to about 6°, is a known procedure for reducing NOx, unfortunately it will by itself cause pollutant generation due to poor combustion. This tradeoff has been troubling the art since emissions control became important. It is an advantage of the invention, that both reduced NOx and other pollutants can be achieved by employing the fuel of the invention in combination with one or more of the above techniques and/or exhaust gas recirculation wherein a portion of the exhaust gas is intermixed with combustion air.
- In operation of the invention in one preferred form an FBC is provided, such as described in U.S. Pat. No. 6,003,303 and the references cited therein.
- The invention has particular utility in the operation of fleet vehicles, which are brought to a central location for refueling at regular intervals, e.g., daily.
- The concentration of FBC catalyst metal in fuel is desirably maintained between 4 and 10 ppm in this exemplary setting.
- The following examples are presented to further illustrate and explain the invention and are not to be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are by weight.
- Cleaner burning biodiesel fuel blends used with the Platinum Plus® fuel borne catalyst (FBC) (added at 0.15 ppm Pt as Pt COD) and a lightly catalyzed (3-5 grams Pt) diesel oxidation catalyst (DOC) produced emission reductions of 51 percent particulates (PM) and 9 percent NOx versus baseline emissions from standard No. 2D fuel. This combination represents a reduction of over 100 lbs per year of regulated pollutants from a typical school bus and over 200 lbs per year for a local delivery vehicle. Typical biodiesel blends can increase NOx by two to four percent.
- Testing was conducted over triplicate federal transient test cycles on a 1995 Navistar DT-466 engine typical of school bus, beverage and local delivery service fleets. The fuels employed are listed in the following table.
LA ULSD with FBC and 20% Fuel No. 2 LA ULSD LA ULSD Bio-Diesel API Gravity 36.36 37.84 39.30 36.0 Sulfur, wt % 0.0323 0.0001 0.00001 0.00034 Cetane Number 47.7 ND ND 55.2 Carbon, wt % 86.84 86.02 86.0 83.7 Hydrogen, wt % 13.16 13.98 14.0 13.6 Aromatics, vol % 29.9 3.26 5.20 ND Olefins, vol % 0.5 ND ND ND Saturates, vol % 69.6 ND ND ND Viscosity at 40 C. 2.3 2.94 3.00 ND (cs) Flash Point, ° F. 157.4 198 188 ND IBP, ° F. 351.1 423 424 430 5%, ° F. 393.3 ND ND 449 10%, ° F. 414.0 455 456 459 20%, ° F. 439.0 ND ND 478 30%, ° F. 459.5 ND ND 493 40%, ° F. 477.9 ND ND 509 50%, ° F. 494.6 500 512 526 60%, ° F. 511.3 ND ND 544 70%, ° F. 529.0 ND ND 567 80%, ° F. 550.4 ND ND 592 90%, ° F. 580.3 563 586 618 95%, ° F. 606.7 ND ND 633 EP, ° F. 641.7 601 624 643 - In the first of two test sequences, a blend of 20 percent biodiesel was combined with low aromatic ultra-low sulfur diesel (LA ULSD) and the Platinum Plus® FBC (0.15% ppm Pt as Pt COD), and the engine was equipped with a lightly catalyzed (3-5 g/ft3) DOC. Here, overall emission reductions were 66 percent HC, 63 percent CO, 9 percent NOx, 51 percent PM and 95 percent SOx. Reductions of over 60 percent were also found in the NO2 fraction of exhaust which is a strong lung irritant and can increase with traditional heavily catalyzed after-treatment devices. The test approach uses a lightly catalyzed DOC which reduces cost and minimizes NO2 formation.
- These tests confirm earlier test work on engines from Cummins and Detroit Diesel, which showed the ability of Cleaner Burning Biodiesel blends made with Platinum Plus® FBC and No. 1D or ULSD to reduce NOx and PM emissions consistently.
- 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 obvious modifications and variations be included within the scope of the present invention which is defined by the following claims. The claims cover the indicated components and steps in all arrangements and sequences which are effective to meet the objectives intended for the invention, unless the context specifically indicates the contrary.
Claims (12)
1. An improved diesel fuel blend comprising biodiesel and low aromatic content ultra-low sulfur diesel fuel.
2. A diesel fuel blend according to claim 1 , which further includes a fuel borne catalyst (FBC) comprising platinum and/or iron, and/or cerium.
3. A diesel fuel blend according to claim 1 , which comprises from 15 to 25% biodiesel.
4. A diesel fuel blend according to claim 1 , wherein the low aromatic ultra-low sulfur diesel fuel component comprises less than 10% by volume aromatics.
5. A diesel fuel blend according to claim 1 , wherein sulfur content is less than 0.0015%.
6. A diesel fuel blend according to claim 5 , wherein the low aromatic ultra-low sulfur diesel fuel component comprises less than 10% by volume aromatics.
7. A diesel fuel blend according to claim 6 , which further includes a fuel borne catalyst (FBC) comprising platinum and/or iron, and/or cerium.
8. A diesel fuel blend according to claim 1 , which comprises from 15 to 25% biodiesel and the low aromatic ultra-low sulfur diesel fuel component comprises less than 10% by volume aromatics and a sulfur content of less than 0.0015% and the blend further includes a fuel borne catalyst (FBC) comprising platinum and/or iron, and/or cerium.
9. An improved diesel fuel blend comprising from 15 to 25% biodiesel and low aromatic content ultra-low sulfur diesel fuel comprising less than 10% by volume aromatics and a sulfur content of less than 0.0015%.
10. A diesel fuel blend according to claim 9 , which further includes a fuel borne catalyst (FBC) comprising platinum and/or iron, and/or cerium.
11. A diesel fuel blend according to claim 10 , wherein the FBC comprises platinum.
12. A diesel fuel blend according to claim 11 , wherein the FBC comprises platinum and iron or cerium.
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
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US11/038,286 US20050160663A1 (en) | 2000-08-01 | 2005-01-19 | Cleaner burning diesel fuel |
CNA2006800087051A CN101163779A (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
BRPI0606588-0A BRPI0606588A2 (en) | 2005-01-19 | 2006-01-19 | diesel fuel combustion cleaner |
KR1020077018826A KR101061708B1 (en) | 2005-01-19 | 2006-01-19 | Cleaner Combustion Diesel Engine |
JP2007552248A JP2008527162A (en) | 2005-01-19 | 2006-01-19 | Clean combustible diesel fuel |
EP06718827A EP1846539A4 (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
SG200803903-4A SG143273A1 (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
RU2007129119/04A RU2360950C2 (en) | 2005-01-19 | 2006-01-19 | Completely burning diesel fuel |
MX2007008819A MX2007008819A (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel. |
CA002595314A CA2595314A1 (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
PCT/US2006/001814 WO2006078763A2 (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
AU2006206467A AU2006206467A1 (en) | 2005-01-19 | 2006-01-19 | Cleaner burning diesel fuel |
ZA200706582A ZA200706582B (en) | 2005-01-19 | 2007-08-07 | Cleaner burning diesel fuel |
NO20074180A NO20074180L (en) | 2005-01-19 | 2007-08-14 | Cleaner burning diesel fuel |
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US22225200P | 2000-08-01 | 2000-08-01 | |
PCT/US2001/024061 WO2002010317A1 (en) | 2000-08-01 | 2001-08-01 | Low-emissions diesel fuel blend |
US10/357,027 US7285140B2 (en) | 2000-08-01 | 2003-02-03 | Low-emissions diesel fuel blend |
US11/038,286 US20050160663A1 (en) | 2000-08-01 | 2005-01-19 | Cleaner burning diesel fuel |
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US10/357,027 Continuation-In-Part US7285140B2 (en) | 2000-08-01 | 2003-02-03 | Low-emissions diesel fuel blend |
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US (1) | US20050160663A1 (en) |
EP (1) | EP1846539A4 (en) |
JP (1) | JP2008527162A (en) |
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CN (1) | CN101163779A (en) |
AU (1) | AU2006206467A1 (en) |
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CA (1) | CA2595314A1 (en) |
MX (1) | MX2007008819A (en) |
NO (1) | NO20074180L (en) |
RU (1) | RU2360950C2 (en) |
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Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2894978A1 (en) * | 2005-12-21 | 2007-06-22 | Total France Sa | Component improving cetane in diesel fuels and useful to prepare diesel fuels, comprises a stearic acid ester comprised e.g. in (a pure state added with a mixture of) vegetable or animal oil esters in crude or partially hydrogenated form |
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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 |
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Cited By (47)
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US20120149952A1 (en) * | 2005-03-21 | 2012-06-14 | Ben-Gurion University Of The Negev Research & Development Authority | Production of diesel fuel from vegetable and animal oils |
FR2894978A1 (en) * | 2005-12-21 | 2007-06-22 | Total France Sa | Component improving cetane in diesel fuels and useful to prepare diesel fuels, comprises a stearic acid ester comprised e.g. in (a pure state added with a mixture of) vegetable or animal oil esters in crude or partially hydrogenated form |
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WO2007077330A3 (en) * | 2005-12-21 | 2007-08-23 | Total France | Cetane improver for diesel fuels and diesel fuels containing it |
US8409304B2 (en) | 2005-12-21 | 2013-04-02 | Total France | Cetane-improving component for diesel fuels and diesel fuels containing it |
FR2894977A1 (en) * | 2005-12-21 | 2007-06-22 | Total France Sa | Component improving cetane in diesel fuels and useful to prepare diesel fuels, comprises a stearic acid ester comprised e.g. in (a pure state added with a mixture of) vegetable or animal oil esters in crude or partially hydrogenated form |
KR101327934B1 (en) | 2005-12-21 | 2013-11-13 | 토탈 라피나쥬 마케팅 | Cetane improver for diesel fuels and diesel fuels containing it |
US20080295394A1 (en) * | 2005-12-21 | 2008-12-04 | Total France | Cetane-Improving Component for Diesel Fuels and Diesel Fuels Containing it |
WO2008066950A3 (en) * | 2006-05-15 | 2009-04-02 | Univ Georgia Res Found | Miscible, multi-component, diesel fuels and methods of bio-oil transformation |
WO2008066950A2 (en) * | 2006-05-15 | 2008-06-05 | University Of Georgia Research Foundation | Miscible, multi-component, diesel fuels and methods of bio-oil transformation |
GB2454635B (en) * | 2006-09-19 | 2011-08-31 | Applied Res Associates Inc | Method of converting triglycerides to biofuels |
WO2008036764A3 (en) * | 2006-09-19 | 2008-09-18 | Applied Res Associates Inc | Method of converting triglycerides to biofuels |
GB2454635A (en) * | 2006-09-19 | 2009-05-20 | Applied Res Associates Inc | Method of converting triglycerides to biofuels |
WO2008036764A2 (en) * | 2006-09-19 | 2008-03-27 | Applied Research Associates, Inc. | Method of converting triglycerides to biofuels |
US20080167823A1 (en) * | 2006-12-22 | 2008-07-10 | Paradigm Sensors, Llc | Impedance spectroscopy (is) methods and systems for characterizing fuel |
US20080172187A1 (en) * | 2006-12-22 | 2008-07-17 | Paradigm Sensors, Llc | Impedance spectroscopy (is) methods and systems for characterizing fuel |
US7947241B2 (en) | 2007-02-23 | 2011-05-24 | Total Raffinage Marketing | Aqueous solution for the treatment of exhaust gases of diesel engines |
US20100015022A1 (en) * | 2007-02-23 | 2010-01-21 | Total Raffinage Marketing | Aqueous solution for the treatment of exhaust gases of diesel engines |
US20090113788A1 (en) * | 2007-11-01 | 2009-05-07 | Martin Reaney | Fuel additive composition to improve fuel lubricity |
US8518128B2 (en) * | 2007-11-01 | 2013-08-27 | University Of Saskatchewan | Fuel additive composition to improve fuel lubricity |
WO2010073233A3 (en) * | 2008-12-23 | 2010-09-30 | Total Raffinage Marketing | Diesel fuel for a diesel engine with high carbon from renewable sources and oxygen contents |
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US20120023811A1 (en) * | 2009-02-26 | 2012-02-02 | Dorivale Holdings Limited | Biodiesel containing non-phenolic additives and thereby possessing enhanced oxidative stability and low acid number |
US20100313467A1 (en) * | 2009-06-16 | 2010-12-16 | Meadwestvaco Corporation | Diesel fuel compositions containing levulinate ester |
US20120216447A1 (en) * | 2009-11-06 | 2012-08-30 | Alternative Petroleum Technologies Sa | Fuels, methods of making them and additives for use in fuels |
WO2013009419A1 (en) * | 2011-07-11 | 2013-01-17 | Phillips 66 Company | Advanced, biomass-derived low-sulfur bunker fuels |
US9511353B2 (en) | 2013-03-15 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst |
US9511350B2 (en) | 2013-05-10 | 2016-12-06 | Clean Diesel Technologies, Inc. (Cdti) | ZPGM Diesel Oxidation Catalysts and methods of making and using same |
US9771534B2 (en) | 2013-06-06 | 2017-09-26 | Clean Diesel Technologies, Inc. (Cdti) | Diesel exhaust treatment systems and methods |
US9545626B2 (en) | 2013-07-12 | 2017-01-17 | Clean Diesel Technologies, Inc. | Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate |
US9511358B2 (en) | 2013-11-26 | 2016-12-06 | Clean Diesel Technologies, Inc. | Spinel compositions and applications thereof |
US9555400B2 (en) | 2013-11-26 | 2017-01-31 | Clean Diesel Technologies, Inc. | Synergized PGM catalyst systems including platinum for TWC application |
US9475005B2 (en) | 2014-06-06 | 2016-10-25 | Clean Diesel Technologies, Inc. | Three-way catalyst systems including Fe-activated Rh and Ba-Pd material compositions |
US9579604B2 (en) | 2014-06-06 | 2017-02-28 | Clean Diesel Technologies, Inc. | Base metal activated rhodium coatings for catalysts in three-way catalyst (TWC) applications |
US9475004B2 (en) | 2014-06-06 | 2016-10-25 | Clean Diesel Technologies, Inc. | Rhodium-iron catalysts |
US9731279B2 (en) | 2014-10-30 | 2017-08-15 | Clean Diesel Technologies, Inc. | Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application |
US9700841B2 (en) | 2015-03-13 | 2017-07-11 | Byd Company Limited | Synergized PGM close-coupled catalysts for TWC applications |
US9951706B2 (en) | 2015-04-21 | 2018-04-24 | Clean Diesel Technologies, Inc. | Calibration strategies to improve spinel mixed metal oxides catalytic converters |
US10533472B2 (en) | 2016-05-12 | 2020-01-14 | Cdti Advanced Materials, Inc. | Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines |
US11053824B2 (en) * | 2016-09-23 | 2021-07-06 | Korea Electric Power Corporation | Exhaust gas purification apparatus and exhaust gas purification method using same |
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 |
US11186789B2 (en) * | 2017-07-18 | 2021-11-30 | Hull Partners, Llc | Biodiesel fuel mixtures |
US11518950B2 (en) | 2017-07-18 | 2022-12-06 | Hull Partners, Llc | Biodiesel fuel mixtures |
US20190031968A1 (en) * | 2017-07-31 | 2019-01-31 | Hull Partners, LLC. | Biodiesel fuel mixtures |
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US11732628B1 (en) | 2020-08-12 | 2023-08-22 | Old World Industries, Llc | Diesel exhaust fluid |
Also Published As
Publication number | Publication date |
---|---|
WO2006078763A2 (en) | 2006-07-27 |
MX2007008819A (en) | 2007-09-27 |
KR101061708B1 (en) | 2011-09-01 |
KR20070099023A (en) | 2007-10-08 |
AU2006206467A1 (en) | 2006-07-27 |
WO2006078763A3 (en) | 2007-09-13 |
EP1846539A2 (en) | 2007-10-24 |
CA2595314A1 (en) | 2006-07-27 |
BRPI0606588A2 (en) | 2009-07-07 |
SG143273A1 (en) | 2008-06-27 |
CN101163779A (en) | 2008-04-16 |
EP1846539A4 (en) | 2009-11-18 |
JP2008527162A (en) | 2008-07-24 |
RU2007129119A (en) | 2009-02-27 |
NO20074180L (en) | 2007-10-11 |
RU2360950C2 (en) | 2009-07-10 |
ZA200706582B (en) | 2008-06-25 |
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