Classifications

• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
  • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
• • C—CHEMISTRY; METALLURGY
  • 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
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
• • 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
  • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
  • F01N2430/04—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by adding non-fuel substances to combustion air or fuel, e.g. additives
• • 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

Definitions

• the invention concerns a new low-emissions diesel fuel based on a base fuel designed for use in jet engines and modified for use in diesel engines, especially of the type used to power buses in metropolitan areas where emissions are of special concern.
• Efforts are being made in many jurisdictions to reduce the emissions of regulated pollutants like unburned hydrocarbons, carbon monoxide, nitrogen oxides (NO x ) and particulates.
• the technologies have included those that modify the combustion conditions and fuels, known as primary measures, and those that treat the exhaust after combustion, known as secondary measures. When effective primary measures are employed, the secondary measures can still be employed to achieve further reductions.
• the invention provides a new low-emissions fuel for use in diesel engines and a method of reducing pollutant emissions from diesel engines.
• the diesel fuel of the invention and its use in diesel engines is described below.
• the invention provides a new diesel fuel comprised of a base fuel, a lubricity additive, a detergent and a bimetallic platinum and cerium fuel additive.
• the invention enhances diesel operation through the use of a low-emissions diesel fuel comprising fungible aviation kerosene, detergent, lubricity additive and a bimetallic, fuel soluble platinum and cerium fuel borne catalyst.
• the low-emissions diesel fuel will comprise fungible aviation kerosene grade 55, 50-300 ppm detergent, 25-500 ppm lubricity additive and as the fuel borne catalyst a combination of 0.01 - 2.0 ppm of a fuel-soluble platinum composition and 2-20 ppm cerium supplied as a fuel soluble cerium composition.
• the preferred detergent 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 TFN-4690-C, at concentrations of from about 50 to 300 ppm in fuel, more narrowly from 75 to 150 ppm, e.g., about 100 ppm, for which they provide the following analysis:
• the preferred lubricity additive comprises tall oil fatty acids, available commercially as mixture of fatty acids including oleic, linoleic and the like. Equivalents which have the same essential function can also be employed. These fatty acids can also be used in dimerized and trimerized forms or blends thereof.
• Dimer acids are high molecular weight dibasic acids produced by the dimerization of unsaturated fatty acids at mid-molecule and usually contain 21-36 carbons. Similarly, trimer acids contain three carboxyl groups and usually 54 carbons. Dimer and trimer acids are generally made by a Diels Alder reaction. This usually involves the reaction of an unsaturated fatty acid with another polyunsaturated fatty acid—typically linoleic acid. Starting raw materials usually include tall oil fatty acids. In addition, it is also known to form dimer and trimer acids by reacting acrylic acid with polyunsaturated fatty acids.
• the product usually comprises a small amount of monomer units, dimer acid, trimer acid, and higher analogs.
• dimer acid i.e., at least about 85% dimer acid
• the reactant product is often merely referred to as dimer acid.
• the individual components can be separated to provide a more pure form of dimer acid or trimer acid by itself.
• Suitable dimer acids for use in this invention include Westvaco Diacid 1550, commercially available from Westvaco Chemicals of Washington Heights, S.C.; Unidyme 12 and Unidyme 14, commercially available from Union Camp Corporation of Dover, Ohio; Empol 1022, commercially available from Henkel Corporation of Cincinnati, Ohio; and Hystrene 3695, commercially available from Witco Co. of Memphis, Tenn.
• blends of dimer and trimer acids can also be used as the lubricity additive of the present invention.
• These blends can be formed by combining dimer and trimer acids, or can comprise the reaction product from the formation of the dimer acid, which can contain substantial amounts of trimer acid.
• blends comprise about 5% to about 80% dimer acid.
• Specific blends include a blend of about 75% dimer acid and about 25% trimer acid, commercially available as Hystrene 3675, a blend of 40% dimer acid and 60% trimer acid, commercially available as Hystrene 5460, and a blend of about 60% dimer acid and about 40% trimer acid, all commercially available from Witco Co. of Memphis, Tenn.
• lubricity additive is available from Texaco as TFN-4769, at concentrations of from about 25 to 500 ppm, e.g., about 50-150 ppm, for which they provide the following analysis:
• the base fuel comprises a commercially-available jet fuel. It can be purchased from Colonial Pipeline Company as "fungible aviation kerosene grade 55". Equivalents which have the same essential function and those varying compositionally by up to 15 %, preferably by less than 5%, can also be employed. It is characterized by the following average analysis:
• cerium III acetylacetonate cerium III napthenate
• cerium octoate and other soaps such as stearate, neodecanoate, and octoate (2-ethylhexoate).
• the cerium is preferred at concentrations of 2 to 20 ppm, more narrowly 4-15 ppm, cerium w/v, i.e., weight of cerium metal in mg to volume of fuel in liters.
• the cerium is supplied as cerium hydroxy oleate propionate complex (40% cerium by weight). Preferred levels are toward the lower end of this range.
• any of the fuel-soluble 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, platinum group metal dibenzylidene acetonates, and fatty acid soaps of teframine platinum metal complexes, e.g., tetramine platinum oleate.
• the platinum group metal is preferred at concentrations of 0.01 - 2.0 ppm platinum w/v, i.e., weight of platinum group metal in mg per volume of fuel in liters. Preferred levels are toward the lower end of this range, e.g., 0.1 -0.5 ppm.
• Platinum COD is the preferred form of platinum for addition to the fuel.
• the low-emissions diesel fuel of the invention comprising a fungible aviation kerosene grade 55, 50-150 ppm detergent, 25-500 ppm lubricity additive and 0.1 -2.0 ppm platinum COD and 5-20 ppm cerium oleate, can improve engine operation in terms of reducing emissions, while maintaining power.
• Retarding engine timing e.g., from 2 to 6°, 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 aviation kerosene in the low-emissions fuel according to the invention can be employed as an emulsion with water, wherein the aviation kerosene 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.
• 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 FBC is optional.
• the fuel thus formed 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.
• 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°
• 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.
• This example describes the preparation of a low-emissions diesel fuel according to a preferred aspect of the invention.
• a fuel is blended using the Colonial Pipeline Company fungible aviation kerosene grade 55 analyzed above, with 100 ppm of the TFA 4690-C detergent, 225 ppm of the noted Texaco lubricity additive and a fuel borne catalyst (FBC) containing 0.15 ppm platinum supplied as platinum COD and 7.5 ppm cerium supplied as cerium hydroxy oleate propionate complex (solution containing 40% cerium by weight).
• FBC fuel borne catalyst
• the fuel was used in a test of a 1998 DDC Detroit Diesel Series 60, 400 hp engine and showed remarkably improved results as compared to a reference on highway No. 2 or a CARB ULSD (California Air Resources Board Ultra Low Sulfur Diesel) fuel. Test data is summarized in the following table, wherein the test results of the FTP transient - composite results are given for the various fuels tested.
• Fuel Sulfur HC CO NOx PM BSFC (ppm) (lbs/hp-hr)
• Example 1 Fuel 300 0.13 0.84 3.66 0.050 0.397

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• 2001
  • 2001-05-08 EP EP01933179A patent/EP1409617A4/de not_active Withdrawn
  • 2001-05-08 CA CA002408907A patent/CA2408907A1/en not_active Abandoned
  • 2001-05-08 WO PCT/US2001/014789 patent/WO2001085876A1/en active Application Filing
  • 2001-05-08 AU AU2001259623A patent/AU2001259623A1/en not_active Abandoned

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