WO1997004045A1 - Procedes permettant de diminuer les emissions toxiques d'un moteur diesel - Google Patents

Procedes permettant de diminuer les emissions toxiques d'un moteur diesel Download PDF

Info

Publication number
WO1997004045A1
WO1997004045A1 PCT/US1996/011908 US9611908W WO9704045A1 WO 1997004045 A1 WO1997004045 A1 WO 1997004045A1 US 9611908 W US9611908 W US 9611908W WO 9704045 A1 WO9704045 A1 WO 9704045A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
platinum group
trap
diesel
group metal
Prior art date
Application number
PCT/US1996/011908
Other languages
English (en)
Inventor
Jeremy D. Peter-Hoblyn
James M. Valentine
Barry N. Sprague
W. Robert Epperly
Original Assignee
Clean Diesel Technologies, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US08/514,978 external-priority patent/US6003303A/en
Application filed by Clean Diesel Technologies, Inc. filed Critical Clean Diesel Technologies, Inc.
Priority to EP96925366A priority Critical patent/EP0854903A4/fr
Priority to AU65489/96A priority patent/AU6548996A/en
Publication of WO1997004045A1 publication Critical patent/WO1997004045A1/fr
Priority to MXPA/A/1998/000511A priority patent/MXPA98000511A/xx

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/029—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles by adding non-fuel substances to exhaust
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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
    • 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
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1208—Inorganic compounds elements
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1225—Inorganic compounds halogen containing compounds
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • 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
    • C10L1/12—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
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
    • 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
    • C10L1/1814—Chelates
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1828—Salts thereof
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • 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
    • 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
    • C10L1/1886—Carboxylic acids; metal salts thereof naphthenic 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
    • 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)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/0025—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D41/0047—Controlling exhaust gas recirculation [EGR]
    • F02D41/0065—Specific aspects of external EGR control
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/04—Heavy metals
    • F05C2201/0418—Noble metals
    • F05C2201/0427—Platinum group, e.g. Pt, Ir

Definitions

  • Catalytic oxidizers have been proposed to reduce the emission of particulates and gaseous hydrocarbons and carbon monoxide from diesel engines. These devices do not trap the particulates, but are primarily intended to oxidize what is referred to as the soluble organic fraction (SOF) of particulates while preferably also oxidizing unburned hydrocarbons and carbon monoxide to reduce emissions of these.
  • SOF soluble organic fraction
  • Flow-through catalytic oxidizers direct the flow of particulates through a maze of catalyzed surfaces which contact the particulates without either trapping them as done by diesel particulate traps or reducing NO x the way triple effect catalysts do for gasoline engines.
  • particulates are increased. For example, when NO x reduction is attempted by modifying engine timing and/or recirculating exhaust gas, particulates are increased. Particulate traps do not directly increase NO XI but have been associated with increased production of carbon monoxide. And, even with a trap, unburned hydrocarbons remain a problem.
  • N0 X1 principally NO and N0 2 , contributes to smog, ground level ozone formation and acid rain.
  • NO is produced in large quantities at the high combustion temperatures associated with diesel engines.
  • the NO 2 is formed principally by the post oxidation of NO in the diesel exhaust stream.
  • Several attempts have been made to reduce NO x , such as by retarding engine timing, exhaust gas recirculation, and the like; however, with current technology, there is a tradeoff between NO x and particulates. For example, exhaust gas recirculation and engine timing changes can reduce the temperature of combustion to thereby decrease NO x formation, but combustion is also affected. When NO x is reduced by these techniques, particulate emissions tend to increase. And, as noted, conditions favoring low emissions of NO x often favor production of increased levels of CO and HC.
  • Traps are reasonably effective for controlling particulates, but uncataiyzed traps increase carbon monoxide and catalyzed traps increase the discharge of SO 3 (adding to the weight of particulates) and suffer from other problems. Traps, of course, don't reduce NO x and efforts made to control NO x must be carefully selected or the result might be to further increase particulates or other products of incomplete combustion.
  • Catalyzed diesel traps are not to be equated with triple-effect catalytic converters of the type used for gasoline engines.
  • Triple-effect catalytic converters of this type simply don't work for diesel engines due to the different manner of operation and the different composition of exhaust gases.
  • the use of diesel traps and the need to improve them has resulted in a great deal of research and a great number of patents and technical publications.
  • the traps are typically constructed of metal or ceramic and are capable of collecting the particulates from the exhaust and withstanding the heat produced by oxidation of carbonaceous deposits which must be burned off at regular intervals.
  • exhaust gas oxidation catalysts can be very effective in reducing carbon monoxide and unburned hydrocarbons, they are either too easily fouled, catalyze the oxidation of SO 2 to SO 3 (which then combines with water and increases the weight of particulates), typically burn off only the soluble organic fraction of the particulates, or have two more of these shortcomings.
  • No catalytic device is known which can collect particulates and burn them off at a practical low temperature while reducing oxidation of S0 2 to S0 3 and also decreasing the emissions of gaseous hydrocarbons and carbon monoxide.
  • the Snider, et al. report also discussed several other approaches, including the use of a fuel additive containing 80 ppm manganese and 20 ppm copper to reduce the regeneration temperature of the trap. While this was effective in reducing the particulate ignition temperature, no measurable reductions in carbon monoxide, unburned hydrocarbons or NO x were noted. Moreover, where Snider, et al., also indicate that precious metal catalysts could be expected to increase the oxidation of SO 2 to SO 3 , these measures do not address an overall solution to the diesel emission problem.
  • U. S. Patent Nos. 5,360,459 and 5,374,154 describe the use of copper-containing organometaUic complexes which, when added to diesel fuel, tend to reduce the ignition temperature of exhaust particulates. Again, these additives do not lower carbon monoxide and unburned hydrocarbons.
  • U. S. Patent No. 4,458,357 describes the use of a fuel additive containing cerium and manganese to reduce the quantity of particulate material necessary to sustain combustion of the particulates on the trap - once combustion is initiated by a glow plug.
  • Patent No. 5,034,020 fuel-soluble platinum additives are disclosed to provide or replenish catalyst metals on a diesel trap to facilitate burning off of trapped particulates.
  • a catalyst comprising platinum, rhodium or rhenium is added directly to a special catalyst chamber, meant to replace a conventional gasoline engine three-way catalytic converter. This patent does not address the issue of particulate emissions from diesel engines. And, again, none of these patents address an overall solution to the diesel emission problem.
  • transition metals were seen to form oxides which foul the traps and cannot be easily removed. They found that the sodium and lithium additives permitted regeneration at temperatures low enough to possibly eliminate the need for supplementary heat, and did, therefore, have some promise in improving trap operation as was achieved previously with the transition metal catalysts. However, they also pointed out that there was no effect on the gaseous components, thus both carbon monoxide and unburned hydrocarbon levels remained higher than would be desired.
  • the invention relates to improvements in reducing emissions of pollutants from diesel engines, preferably equipped with a diesel particulate trap, by providing platinum group metal catalysts in the exhaust gases of the engines. This is variously accomplished by adding the platinum group metal catalyst, such as part of an additive composition containing a platinum group metal catalyst composition, either alone or with an auxiliary catalytic metal, to the diesel fuel, to the combustion air, or to the exhaust or combustion gases.
  • the platinum group metal catalyst such as part of an additive composition containing a platinum group metal catalyst composition, either alone or with an auxiliary catalytic metal
  • diesel emissions of NO x and particulates are reduced, simultaneously with gaseous hydrocarbons and carbon monoxide, by the combined use of exhaust gas recirculation, a particulate trap, and a platinum group metal catalyst composition, alone or with an auxiliary catalytic metal.
  • diesel emissions of NO x and particulates are reduced, simultaneously with gaseous hydrocarbons and carbon monoxide, by the combined use of retarding engine timing, a particulate trap, and a platinum group metal catalyst composition, alone or with an auxiliary catalytic metal.
  • a multi-metal catalyst composition comprising a combination of a platinum metal catalyst composition and at least one auxiliary catalyst metal, is added to the diesel fuel prior to combustion to provide catalyst metal to the exhaust system including a diesel trap to lower the balance point of the particulate trap (the temperature at which the rate of trap loading equals the rate of regeneration) while also lowering the emissions of carbon monoxide and unburned hydrocarbons.
  • the results in both embodiments are achieved while, preferably, selectively maintaining a low oxidation of S0 2 to SO 3 .
  • the first embodiment comprises: adding a platinum group metal composi ⁇ tion and a cerium compound to a diesel fuel in an effective amount to lower the emissions of unburned hydrocarbons and carbon monoxide and to lower the temperature at which particulates are burned from the trap; operating the diesel engine by burning the fuel over a sufficient period of time to produce exhaust gases and achieve a sustained reduction in unburned hydrocarbons and carbon monoxide; and passing the exhaust gases from the operation of the engine through the diesel trap whereby particulates are collected in the trap and burned therein at a temperature lower than could be achieved in the absence ofthe platinum group metal and the cerium.
  • the operation of a diesel engine is improved by lowering the emissions of unburned hydrocarbons and carbon monoxide, comprising: providing a diesel fuel and combustion air; providing a platinum group metal catalyst composition selected from the group consisiting of alcoholates, sufonates, beta-diketonates, soaps, and mixtures of these; combusting the fuel in a diesel engine to produce exhaust gases; and, directing exhaust gases into an exhaust system, wherein the platinum group metal catalyst composition is introduced into the fuel, exhaust gases or combustion air, in amounts effective to provide platinum group metal in the exhaust system at a level of up to 1 ppm based on the volume of fuel burned to produce the exhaust gases.
  • the invention provides a method for operating a diesel engine with reduced emissions of NO x , particulates, gaseous hydrocarbons and carbon monoxide, comprising: providing a diesel engine and a source of diesel fuel; providing a combustion air mixture including incoming air and exhaust gases from a previous combustion cycle of the engine; providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition comprising cerium; introducing the combustion air mixture into the cylinder of a diesel engine; compressing the combustion air within the cylinder; injecting the diesel fuel into the cylinder of a diesel engine; combusting the fuel to produce exhaust gases; directing the exhaust gases into an exhaust system including a diesel trap to remove particulates from the exhaust gases; and, mixing a portion of the exhaust gases with incoming combustion air to provide a combustion air mixture for a subsequent combustion cycle; wherein the amount of exhaust gases present in the combustion air mixture in the cylinder of the diesel engine is effective to lower the production of NO x by the engine utilizing said combustion air mixture as compared to combustion air
  • the invention provides in another of its aspects, a method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO ⁇ ) unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising: providing a diesel engine and a source of diesel fuel; providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition containing copper and/or cerium; introducing combustion air into the cylinder of a diesel engine; compressing the combustion air within the cylinder; injecting the diesel fuel into the cylinder of a diesel engine, the injection timing of the diesel engine being set in a manner designed to reduce the nitrogen oxides emissions from the engine after combustion of a diesel fuel; combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and an auxiliary catalytic metal; and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases, wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition
  • Also provided by the invention is a method for improving the operation of a diesel engine exhaust system comprising: adding a platinum group metal composition and at one least auxiliary catalytic metal composition selected from the group consisting of compounds of sodium, lithium, potassium, calcium, magnesium, cerium, iron, copper, manganese, and mixtures of these, to a diesel fuel in effective amount such that exhaust produced by combustion catalyzes the exhaust system including a diesel trap effectively to lower the emissions of unburned hydrocarbons and carbon monoxide; operating a diesel engine by burning the fuel; and passing the exhaust from the operation of the engine through the exhaust system including the diesel trap to reduce emissions of hydrocarbons and carbon monoxide and reduce the balance point for a trap.
  • the invention provides a method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO x , unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising: providing a diesel engine and a source of diesel fuel; providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition containing cerium; introducing combustion air into the cylinder of a diesel engine; compressing the combustion air within the cylinder; injecting the diesel fuel into the cylinder of a diesel engine, thereby combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and cerium catalyst; and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases, wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition are introduced into the fuel, exhaust gases or combustion air, in amounts effective to provide sufficient platinum group metal and cerium catalyst in the exhaust system to lower the balance point temperature of part
  • the invention provides a method for improving the operation of a diesel engine including a diesel trap by lowering the emissions of NO x , unburned hydrocarbons and carbon monoxide, while also reducing the balance point of the trap, the method comprising: providing a diesel engine and a source of diesel fuel; providing a platinum group metal catalyst composition and an auxiliary catalytic metal composition selected from the group consisting of compounds of sodium, lithium, potassium, calcium, magnesium, cerium, iron, copper, manganese, and mixtures; introducing combustion air into the cylinder of a diesel engine; compressing the combustion air within the cylinder; injecting the diesel fuel into the cylinder of a diesel engine, thereby combusting the fuel to produce exhaust gases containing particulates and platinum group metal catalyst and auxiliary catalytic metal; and, directing exhaust gases into an exhaust system including a diesel trap which removes at least a portion of the particulates from the exhaust gases, wherein the platinum group metal catalyst composition and the auxiliary catalytic metal composition are introduced into the fuel,
  • the exhaust system in each of the embodiments will be selectively catalyzed, meaning that it will have the designated advantages in terms of hydrocarbon and carbon monoxide reduction while causing less conversion of SO 2 to S0 3 than a trap catalyzed with platinum prior to operation.
  • the platinum group metal catalyst can be added in any manner effective, such as by adding it to the fuel in bulk storage, to the fuel in a tank associated with the engine, or by continuous or intermitent addition, such as by a suitable metering device, into: the fuel line leading to the engine, or in the form of a vapor, gas or aerosol into the air intake, the exhaust gases before the trap, exhaust gases after the trap but before recirculation to the engine, or a mixing chamber or equivalent means wherein the exhaust gases are mixed with incoming air.
  • the platinum group metal catalyst composition is preferably employed at a level of less than 1 part by weight of platinum group metal per million parts by volume fuel (ppm).
  • ppm platinum group metal per million parts by volume fuel
  • all "parts per million” figures are on a weight to volume basis, i.e., grams/million cubic centimeters (which can also be expressed as milligrams/liter), and percentages are given by weight, unless otherwise indicated.
  • the auxiliary catalyst metal composition can be employed to deliver the auxiliary catalyst metal at suitable levels, e.g., from about 1 to about 100 ppm and preferably 20 to 60 ppm of the catalyst metal in combination with the platinum group metal composition in diesel fuels. It is preferred to add the platinum group metal catalyst and the auxiliary catalyst metal to the fuel in amounts effective to reduce the balance point temperature of the trap by at least 50°C, and preferably by at least 150°C.
  • Figure 1 is a schematic view of an embodiment of the invention wherein a portion of the exhaust gas, produced by the combustion of diesel fuel catalyzed with at least a platinum group metal catalyst composition, is recirculated to the combustion chamber of the illustrated diesel engine to lower NO x and achieve an overall reduction of polluting emissions;
  • Figure 2 is a chart which presents a summary of results from the tests of Example 1 , comparing baseline and final results on carbon monoxide emissions both following a particulate trap and in an exhaust system which bypasses a trap;
  • Figure 3 is a chart, similar to that of Figure 2, but showing the results for hydrocarbon emissions
  • Figure 4 is a chart, similar to that of Figure 2, but summarizing the results for particulate emissions
  • Figure 5 is a graph showing the efficiency of hydrocarbon conversion for the present invention as compared to other test systems
  • Figure 6 is a graph, similar to that of Figure 5, but showing the selectively of the invention on sulfur conversion.
  • Figure 7 is a graph presenting the data for Figures 5 and 6 to illustrate the tradeoff between sulfur and hydrocarbon conversion.
  • diesel engines is meant to include those engines capable of being run on “diesel fuel”, as defined by the American Society of Testing and Management (ASTM) Standard Specification for Fuel Oils (designation D 396-86) or any of grade numbers 1-D, 2-D or 4-D, as specified in ASTM D 975.
  • diesel fuel can be a fuel oil No. 2 or No. 4 petroleum distillates as well as alternative diesel fuels containing emulsified water or alcohols such as ethanol or methanol, very low sulfur fuels (less than 0.05% sulfur), diesel fuel blends with bioderived components (animal and vegetable fats and oils, fractions and derivatives), and the like, as long as they exhibit volatility and cetane number characteristics effective for the purpose.
  • Diesel fuels will typically have a 90% distillation point within the range of 300° to 390°C and a viscosity of from 1 to 25 centistokes at 40°C.
  • the invention concems diesel engines equipped with or having associated therewith a diesel engine particulate trap.
  • a diesel engine particulate trap is disposed such that the exhaust stream from the engine passes therethrough.
  • a diesel engine particulate trap (also referred to herein as a "diesel trap”) is disposed in the exhaust system, typically on the tailpipe of the vehicle in which the diesel engine is located, downstream from the exhaust manifold. While generally known to those skilled in the art, reference to Figure 1 may help further illustrate a representative configuration.
  • Suitable diesel traps are known to the skilled worker and generally comprise an apparatus designed to trap or collect particulates which are present in the exhaust stream of the diesel engine.
  • a trap can be made of any suit- able material such as ceramic (for instance, a cordierite ceramic material), glass fiber, or metal.
  • the trap can be coated with a catalytic material to facilitate regeneration. It is an advantage of the present invention that the traps are selectively catalyzed during operation.
  • Suitable diesel engine particulate traps are typically constructed of a gas permeable material, such as a ceramic. Traps can be configured to include at least two (and generally several) parallel gas channels longitudinally arranged in a honeycomb-type structure extending between what can be referred to as an upstream, or engine-side, face and a downstream, or exhaust-side, face. Each passage is plugged at one of its faces such that altemate faces of adjacent passages are plugged. In this way, exhaust entering the trap through a passage at its unplugged upstream face must pass through a wail into an adjacent passage in order to exit the trap from its unplugged downstream face. Particu ⁇ lates in the exhaust are then trapped or collected on the wall.
  • a trap is described, for instance, in U.S. Patent 4,568,357 to Simon, the disclosure of which is inco ⁇ orated herein by reference.
  • the particulate trap used in the methods of the invention can be one which is self regenerating, that is, trapped particulates are ignited by heat derived from the engine, usually from the hot exhaust gasses themselves. In order to reduce particulate buildup on the trap, it is desired that the particulates are combusted or "burned off" the trap in order to free the surface thereof for further collection of particulates. Under normal conditions, and without the use of a catalyst, temperatures of from over about 500°C up to about 600°C, and sometimes more, are required to combust the particulates and, thus, regenerate the trap. Since a four stroke diesel engine produces exhaust gases which are typically exhausted at an average temperature of between about 400 °C and
  • the invention improves the operation of diesel engines equipped with traps, either catalyzed or uncatalyzed, and if catalyzed in any stage of activity.
  • the regeneration characteristics of the trap are improved by lowering the balance point of the trap.
  • the invention lowers the temperature of the trap whereat a steady state is achieved and the rate of particulate deposit in the trap is the same as the rate of particulate burning in the trap.
  • the balance point can be determined by plotting against temperature, the incremental change in temperature divided by the incremental change in pressure through the trap.
  • the temperature at the point where the plotted line crosses the abscissa can be taken as the balance point and is used to define that term for the purposes of this description.
  • the invention enables the balance point to be lowered sufficiently to permit reliable trap regeneration, and to do so with reductions in carbon monoxide and unburned hydrocarbons.
  • the art has not previously been able to achieve such significant results in these apparently contradictory effects.
  • no auxiliary heater is needed to achieve continuous regeneration during sustained operation of the diesel engine.
  • the benefits achievable for the platinum group metals are not adversely affected by the presence of auxiliary catalysts, making it possible to obtain the positive benefits of both the platinum group metal catalyst and the auxiliary catalyst.
  • diesel emissions of NO x and particulates are reduced simultaeously, and simultaneously with gaseous hydrocarbons and carbon monoxide, by the combined use of exhaust gas recirculation, a particulate trap, and a platinum group metal catalyst composition alone or in combination with an auxiliary catalyst.
  • Figure 1 is provided to illustrate this embodiment wherein the catalyst compositions are added to the diesel fuel.
  • diesel emissions of NO x and particulates are reduced simultaneously, and simultaneously with gaseous hydrocarbons and carbon monoxide, by the combined use of retarding engine timing, a particulate trap, and a platinum group metal catalyst composition alone or in combination with an auxiliary catalyst.
  • a multi-metal catalyst composition comprising a combination of a platinum metal catalyst composition and at least one auxiliary catalyst metal, can be added to the diesel fuel prior to combustion to provide catalyst metal to the exhaust system including a diesel trap to lower the balance point of the particulate trap while also lowering the emissions of carbon monoxide and unburned hydrocarbons.
  • One or both of the catalyst metal compositions can alternatively introduced into the combustion air or exhaust at any point effective to provide active metal catalysts in the trap.
  • Platinum group metals include platinum, palladium, rhodium, ruthenium, osmium, and iridium.
  • Compounds including platinum, palladium, and rhodium, especially compounds of platinum alone or in combination with rhodium and/or palladium compounds are preferred in the practice of this invention since the vapor pressure of these metals is sufficiently high to facilitate the desired reduction of carbon monoxide emissions.
  • the platinum group metal catalyst compositions can be of the type which are soluble in nonpolar hydrocarbon fuels, soluble in polar fuels such as those including methanol, ethanol, or other lower alkyl alcohols, or soluble in fuels having polar and nonpolar components such as emulsified fuels and gasohol.
  • the platinum group metal catalyst compositions can be formulated according to the teachings below or as known to the art generally, to have the degree of stability necessary to assure that the platinum group metal catalyst composition is subjected to the heat of combustion in the combustion chamber within a cylinder of a diesel engine to release the platinum group metal catalyst into the exhaust gases which transport it to the exhaust system wherein it is-deposited in the trap along with the particulates and any auxiliary catalyst metal.
  • the platinum group metal catalyst compositions can be fuel-soluble, fuel- soluble but water-sensitive, or water-soluble, as will be described below.
  • the platinum group metal catalyst compositions are typically added in amounts effective to provide concentrations of the platinum group metal relative to the fuel of less than 1 part per million (ppm).
  • the auxiliary catalytic metal compositions are preferably used in amounts to provide concentrations of from about 1 to about 100 ppm of the metal. Simultaneous Reduction of NO x and Particulates
  • the combination of a particulate trap and a fuel additive comprising at least a platinum group metal composition in catalytic amounts is employed along with a technique to control NO x emissions, such as exhaust gas recirculation or retarding engine timing.
  • a technique to control NO x emissions such as exhaust gas recirculation or retarding engine timing.
  • Figure 1 illustrates in schematic form the process of exhaust gas recirculation as improved by the invention, such that a significant improvement is made on the overall diesel emission problems - reducing NO x , carbon monoxide, gaseous unburned hydrocarbons, and particulates.
  • Figure 1 shows a diesel engine 10 having an exhaust manifold 20 directing the exhaust from the engine to an exhaust system including a diesel trap 30.
  • the diesel engine is supplied with fuel from tank 40 via line 42 and fuel injectors 44', 44", 44"', and 44"".
  • the fuel tank includes diesel fuel including a platinum group metal catalyst composition, although this composition could be supplied from a separate canister fitted to the fuel line or from a suitable metering pump. It can also be supplied in the form of an aerosol into either the intake air in line 24, the exhaust manifold 20, a exhaust line leading to the trap, or recycle line 22.
  • Figure 1 shows line 22 connected to exhaust line 32 to divert a portion of the exhaust gases from line 32 and recirculates it to chamber 26 for mixing with combustion air fed to the combustion chambers ofthe cylinders ofthe engine 10.
  • the portion of exhaust gases separated from manifold exhaust line 32 can be mixed with incoming air by suitable means (not shown) such as described by Showalter in U. S. Patent No. 4,609,342, or the like.
  • the process of this embodiment requires the provision of a diesel fuel, such as in tank 40, comprising a platinum group metal catalyst composition. Consistent with the other embodiment of the invention, it can also include an auxiliary catalyst metal as will be described in detail below.
  • a portion of the exhaust gases from a previous combustion cycle of the engine are diverted from exhaust line 32 by line 22 and mixed with incoming combustion air from line 24. The combustion air and the separated exhaust gases are thoroughly mixed.
  • the resulting combustion air mixture is introduced into the cylinders of the diesel engine and distributed such as at port 28 (the other cylinders are illustrated with similar, but unnumbered ports).
  • the combustion air mixture is compressed in nomal fashion for a diesel engine within each cylinder.
  • the diesel fuel (preferably catalyzed as described) is then injected into the cylinders.
  • the fuel is then combusted with the combustion air mixture (typically at an excess oxygen content of from about 2 to about 15%) to produce exhaust gases including platinum group metal (and any auxiliary catalyst metal, if employed).
  • the amount of exhaust gases recirculated to chamber 26 for forming the combustion air will be effective to lower the production of NO x by the engine utilizing the combustion air mixture as compared to combustion air not containing exhaust gases. Typically, from about 1 to about 20% can be efficiently recirculated.
  • the platinum group metal catalyst is preferably present in the diesel fuel in an amount effective upon combustion ofthe diesel fuel to provide sufficient platinum group metal in the exhaust system to lower the emissions of unburned hydrocarbons and carbon monoxide. This will be less than about 1 ppm, based on the weight of the catalyst metal, and will preferably be within the range of from about 0.05 to about 0.5 ppm, and most preferably in the range of from 0.10 to 0.30 ppm.
  • the injection timing of a diesel engine is set (for instance retarded or set during manufacture of the engine) in a manner designed to reduce the nitrogen oxides emissions from the engine after combustion of a diesel fuel.
  • the injection timing should be set at that level sufficient to reduce nitrogen oxides levels to those desired generally according to either preset arbitrary limits or those required by various regulatory authorities. For instance, in some jurisdictions, it is required that diesel engines (notably new engines) emit no more than 4 grams per brake horsepower-hour (gm/BHP-hr) of nitrogen oxides. Although not always possible, reduction of NO x levels to no greater than about 4 gm/BHP-hr is, therefore, desired.
  • injection timing can be retarded by between about 0.5° and about 8° to secure the advantages of the present invention. More particularly, the engine timing can be retarded between about 2° and about 6° in order to achieve satisfactory reductions in nitrogen oxides levels without compromising fuel consumption or CO or unburned hydrocarbon emissions to a level beyond that for which at least partial compensation is possible. If, for example, the injection timing is initially set at 18° before top dead center, practice of this invention dictates that it is preferably retarded, by which is meant injection occurs closer in time to top dead center, to about 17.5° to about 10°, more preferably about 16° to about 12°, before top dead center.
  • the injection timing can be set by retarding the timing of the engine during maintenance or at any other time when access to the engine is possible.
  • the injection timing can be set by having it initially set at the desired level during manufacture or otherwise prior to placing the engine into operation.
  • the use of the noted additives can increase fuel efficiency (i.e., reduce fuel consumption) to levels observed before the retarding of the injection timing to achieve NO x reductions.
  • This can be achieved by this invention (using catalysts and a trap) while reducing emissions of carbon monoxide and unburned hydrocarbons, which are often increased by adding traps.
  • a suitable oxidizer (either precatalyzed or catalyzed by the operation of the invention), such as a matrix of extrudate or pellets of alumina or other refractory oxide, or a monolith having a surface of a refractory oxide or a metal matrix, can also be utilized.
  • a suitable oxidizer such as a matrix of extrudate or pellets of alumina or other refractory oxide, or a monolith having a surface of a refractory oxide or a metal matrix
  • a diesel engine having a diesel engine particulate trap disposed such that the exhaust stream from the engine passes therethrough.
  • the diesel engine particulate trap is disposed downstream from the exhaust manifold.
  • a diesel trap can help to at least partially eliminate the particulates generated by retarding the injection timing.
  • the additive can also decrease the ignition temperature of particulates collected on the trap. This can facilitate regeneration of the trap for greater efficiency. It is an advantage of the invention that the benefits achievable for the platinum group metals (including reductions in hydrocarbons, carbon monoxide, and trap balance point temperature) are not adversely affected by the presence of auxiliary catalysts, making it possible to obtain the positive benefits of both the platinum metal catalyst and the auxiliary catalyst.
  • platinum group metal catalyst compositions are those which are soluble in the typical diesel fuel which is essentially a nonpolar hydrocarbon fuel, but can contain tramp moisture in amounts which would destabilize some fuel-soluble platinum group metal compositions.
  • hydrocarbon-fuel-soluble organometaUic platinum group metal coordination compounds are any of those disclosed for example in prior U.S. Patent Nos.
  • a blend of these compounds can be used with one or more other platinum group metal compounds such as soaps, acetyl acetonates, alcoholates, ⁇ -diketonates, and sulfonates, e.g., of the type which will be described in more detail below.
  • the composition will be temperature stable, and substantially free of phosphorus, arsenic, antimony, or halides.
  • the platinum group metal catalyst composition will also be substantially insensitive to water, as evidenced by a partition ratio sufficient to maintain signifi ⁇ cant preferential solubility in the fuel.
  • the relative solubility of the composition in the diesel fuel and water is important since there is often a substantial amount of water admixed in with fuel, and any platinum group metal catalyst composition which separates from the fuel can precipitate out or be lost as a coating on fuel system walls.
  • the relative solubility of the composition in the fuel is referred to herein as the "partition ratio" and can be expressed as the ratio of the amount in milligrams per liter of composition which is present in the fuel to the amount which is present in the water. This can most easily be determined in a 100 milliliter (ml) sample which is 90% fuel and 10% water. By determining the amount of composition in the fuel and the amount in the water, the partition ratio can be readily determined.
  • the organic nature of the platinum group metal compositions of this type provides solubility in nonpolar hydrocarbon fuels such as diesel fuel, thereby facilitating the introduction of the composition into the combustion chamber of an internal combustion engine.
  • High fuel solubility maintains the platinum in the fuel and inhibits its precipitation or plating out in the fuel tank or fuel lines prior to introduction into the combustion chamber.
  • high fuel solubility and stability in solution are important.
  • lesser stabilities can be effective.
  • Temperature stability of the composition is important in many practical and operational contexts.
  • a fuel additive is often packaged and stored in a building or in a delivery truck for extended periods of time during which the additive can be exposed to temperature variations and extremes. If the breakdown temperature of the composition is not sufficiently high (i.e., if the composition is not temperature stable at the temperatures to which it is expected to be exposed), then the packaged composition as part of an additive will quickly break down and become virtually useless.
  • the breakdown temperature of the platinum group metal catalyst composition should be at least about 40°C, preferably at least about 50°C, in order to protect against most temperatures to which it can be expected to be exposed. In some circumstances, it will be necessary that the breakdown temperature be no lower than about 75°C.
  • the organic nature of the preferred platinum group metal catalyst compositions helps to maintain them in solution in an organic solvent which provides a convenient diluent and can have functional properties, thereby preventing "plating out” of the platinum group metal catalyst composition in the packaging medium.
  • the platinum group metal catalyst composition should be substantially free from objectionable amounts (in some cases, traces) of compounds or functional groups containing, phosphorus, arsenic, antimony, and, especially, halogens (i.e., they should not contain a substantial amount of such functional groups) which have significant disadvantages like "poisoning" or otherwise reduc ⁇ ing the effectiveness of the platinum group metal catalyst composition or any auxiliary catalyst metal composition employed.
  • Halogens can have the additional undesirable effect of rendering a platinum group metal more volatile, leading to its release from the exhaust system.
  • the purified platinum group metal catalyst composition contains no more than about 300 ppm of halogen nor more than 500 ppm (on a weight per weight basis) of phosphorus, arsenic, or antimony, more preferably no more than about 250 ppm of any of these.
  • the additive contains no phosphorus, arsenic, or antimony.
  • the platinum group metal catalyst composition can be prepared in a process which utilizes precursors or reactant compositions having a minimum of such functional groups; or the composition can be purified after preparation. Many such methods of purification are known to the skilled worker.
  • the preferential solubility of the composition in fuel as compared to water can be critical because if a substantial amount of the composition is dissolved in the water which may be present, the overall effectiveness of the composition is proportionally reduced.
  • This partition ratio should be at least about 25 and is most preferably greater than about 50.
  • the composition have at least one platinum group metal-to-carbon covalent bond.
  • a platinum group metal-to-oxygen or platinum group metal-to-nitrogen bond can be acceptable, but there must also be at least one metal to carbon bond.
  • the preferred class of fuel soluble catalyst compositions includes compounds where the platinum group metal exists in oxidation states II and IV.
  • Compounds in the lower (II) state of oxidation are preferred due to their function in generating the catalytic effect, preferably having at least one coordination site occupied by a functional group containing an unsaturated carbon-to-carbon bond. Most preferably, two or more of the coordination sites will be occupied by such functional groups since the stability and solubility in diesel fuel of compounds having such multiple functional groups are improved.
  • Benzene and analogous aromatic compounds such as anthracene and naphthalene.
  • Cyclic dienes and homologues such as cylooctadiene, methyl cyclopentadiene, and cyclohexadiene.
  • Olefins such as nonene. dodecene, and poiyisobutenes.
  • Acetylenes such as nonyne and dodecyne.
  • unsaturated functional groups in turn, can be substituted with nonhalogen-substituents such as alkyl, carboxyl, amino, nitro, hydroxyl, and alkoxyl groups.
  • nonhalogen-substituents such as alkyl, carboxyl, amino, nitro, hydroxyl, and alkoxyl groups.
  • Other coordination sites can be directly occupied by such groups.
  • compositions A preferred group of compositions is represented by the following general formula
  • L 1 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands, preferably cycloocta- dienyl;
  • M is a platinum group metal, especially platinum itself; and
  • R 1 and R z are each, independently, substituted or unsubstituted lower alkyl (e.g., 1-5 carbons) benzyl, nitrobenzyl, aryl, cyclopentadiene or pentamethyl cyclopentadiene, pref- erably benzyl, methyl and/or phenyl.
  • Exempiary of compounds are dipyridine platinum dibenzyl; bipyridine platinum dibenzyl; dipyridine palladium diethyl; cyclooctadiene platinum dimethyl; cyclooctadiene platinum diphenyl; cyclooctadiene platinum dibenzyl; cyclooctadiene platinum dinitrobenzyl; cyclooctadiene platinum methyl cyclopentadiene; norbornadiene platinum di-cyciopentadiene; dimethyl platinum cyclooctatetrene (which often assumes the formula dimethyl platinum cyclooctatetrene platinum dimethyl); and cyclooctadiene osmium bis (cyclopentadiene).
  • the most preferred platinum group coordination compounds according to the above general formula are those represented by the foilowing formula:
  • X is a cyclooctadienyl ligand
  • M is a platinum group metal
  • R is methyl, benzyl, phenyl, or nitrobenzyl.
  • the R group can be any organic group which provides the requisite stability and can be substituted consistently with this objective.
  • piatinum group metal compounds are the following:
  • M is a platinum group metal
  • R and R 2 are lower alkyl, e.g., from 1 to 10 carbons
  • each n is, independently, an integer from 1 to 5.
  • Representative of this group is 2.2'-bis(N,N-dimethylamino)1 ,1'-diphenyl palladium.
  • M is a platinum group metal
  • R is a lower alkyl, e.g., from 1 to 5 carbons
  • R 2 is a cycloalkene having, e.g., from 5 to 8 carbons and from 2 to four unsaturations within the ring structure.
  • this group is tetrakis (methoxy carbonyl) palladia cyclopentadiene.
  • M is a platinum group metal and ⁇ is phenyl.
  • ⁇ is phenyl.
  • ⁇ is phenyl.
  • M is a platinum group metal
  • R 2 are lower alkyl, e.g., having from 1 to 5 carbons. Representative of this group is diethyl dipyridyl palladium.
  • M is a platinum group metal and R is hydrogen, aryl, or alkyl, e.g., one to ten carbons. Representative of this group is bis (phenyl allyl) palladium.
  • G compositions of the general formula
  • L 2 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands
  • M 1 is a platinum group metal, especially rhodium or iridium
  • R 3 is cyclopentadiene or pentamethyl cyclopentadiene.
  • Exemplary of suitable compounds of the formula L 2 M 1 R 3 are cyclooctadiene rhodium cyclopentadiene; cyclooctadiene rhodium pentamethyl cyclopentadiene; norbornadiene rhodium pentamethyl cyclopentadiene; cyclooctadiene iridium cyclopentadiene; cyclooctadiene iridium pentamethyl cyclopentadiene; norbornadiene iridium cyclopentadiene; and norbornadiene iridium pentamethyl cyclopentadiene.
  • L 3 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous monodentate ligands
  • M 2 is platinum, palladium, rhodium, or iridium
  • R 4 is COOR 5 , wherein R 5 is hydrogen or alkyl having from 1 to 10 carbons, preferably methyl.
  • Exemplary compounds have the structure
  • R 4 such as tetrakis (methoxy carbonyl) palladia cyclopentadiene (wherein L 3 is cyclopentadiene, M 2 is palladium, and R 4 is COOH 3 ).
  • L 4 is a non-nitrogenous cyclic polyolefin ligand, preferably cyclooctadiene or pentamethyl cyclopentadiene
  • M 3 is platinum or iridium
  • R 6 is benzyl, aryl, or alkyl, preferably having 4 or more carbons, most preferably phenyl.
  • Exemplary of compounds having the general formula L 4 M 3 (COOR 5 ) 2 are cyclooctadiene platinum dibenzoate dimer; and pentamethyl cyclopentadiene iridium dibenzoate.
  • compositions comprising a reaction product of [L 5 RhX] 2 and R 7 MgX wherein L 5 is a non-nitrogenous cyclic polyolefin ligand, preferably cyclooctadiene or pentamethyl cyclopentadiene; R 7 is methyl, benzyl, aryl, cyclo ⁇ pentadiene or pentamethyl cyclopentadiene, preferably benzyl or phenyl, and X is a halide.
  • L 5 is a non-nitrogenous cyclic polyolefin ligand, preferably cyclooctadiene or pentamethyl cyclopentadiene
  • R 7 is methyl, benzyl, aryl, cyclo ⁇ pentadiene or pentamethyl cyclopentadiene, preferably benzyl or phenyl
  • X is a halide.
  • Functional groups which are especially preferred for use as ligands L 1 through L 3 are neutral bidentate ligands such as cyclopentadiene, cyclooctadiene, pentamethyl cyclopentadiene, cyclooctatetrene, norbornadiene, o-toluidine, o-phenantholine, and bipyridine. Most preferred among monodentate ligands is pyridine.
  • R 8 is aryl or alkyl; and R 9 is aryl, preferably phenyl.
  • M 4 is platinum group metal, especially rhodium or iridium; n is 2 for platinum and palladium, and 3 for rhodium, iridium, osmium and ruthenium; and R 10 is hydrogen, aryl, or alkyl.
  • One compound of this type is bis (phenyl allyl) palladium.
  • R “PtR 12 wherein R 11 is aryl, alkyl or mixtures thereof, such as cyclopentadiene or pentamethyl cyclopentadiene; and R 12 is hydroxyl (-OH), acetylacetonate (-CH 2 (COCH 3 ) 2 ), cyclopentadiene or pentamethyl cyclopentadiene (exemplary of which is trimethyl platinum hydroxide).
  • L 6 is substituted or unsubstituted butadiene or cyclohexadiene; M 5 is rhodium or iridium; and R 13 is cyclopentadiene or pentamethyl cyclopentadiene (exemplary of which are butadiene rhodium cyclopentadiene and butadiene iridium cyclopentadiene.
  • platinum group metal catalyst compositions which would normally be taken up or destabilized by any water present.
  • These platinum group metal catalyst compositions can be either simply water-sensitive or essentially water-soluble.
  • Water-sensitive platinum group metal catalyst compositions are characterized as being instable in the presence of from about 0.01 to about 0.5% water, but having sufficient affinity for the fuel that when a water-functional composition is employed, they remain in the fuel and effective for their intended catalytic function.
  • platinum group metal catalyst compositions in this group are, alcoholates, sufonates, substituted and unsubstituted beta-diketonates and soaps selected from the group consisting of stearates, palmitates, laurates, tallates, napthanates, other fatty acid soaps, and mixtures of two or more of these.
  • the water-sensitive compounds typically exhibit partition ratios of from about less than 50, down to about 1.
  • Compositions of this type having partition ratios as low as 40 and below, e.g., less than 25, and more narrowly less than 1 to 20, can be effective according to the invention.
  • essentially water-soluble platinum group metal catalyst compositions having partition ratios of less than 1 can be employed according to the invention.
  • the fuels are formulated to include a water-functional composition selected from the group consisting of lipophilic emulsifiers, lipophilic organic compounds in which water is miscible, and mixtures of these, which can be added to the fuel as an additive including any catalyst compositions, as a discrete additve or as part of the bulk fuel.
  • the preferred compounds or compositions have the capability of preventing frank separation of water from the fuel and maintain it tied up in the fuel, preferably in complete miscibility with a nonpolar fuel component or in droplets no larger than about 2 ⁇ , and preferably smaller than about 1 ⁇ in diameter, based on a weight average of droplet sizes. Discrete pockets or pools of water, where the uniform distribution of the platinum group metal catalyst composition within the fuel is disturbed, are preferably avoided.
  • a suitable hydrocarbon diluent such as any of the higher aliphatic alcohols (e.g., having over 3 carbons, i.e., from 3 to 22 carbons), tetrahydrofuran, methyl tertiarybutyl ether (MTBE), octyl nitrate, xylene, mineral spirits or kerosene, in an amount effective to provide a suitably pourable and dispersible mixture for additive compositions.
  • MTBE methyl tertiarybutyl ether
  • octyl nitrate e.g., tetrahydrofuran
  • MTBE methyl tertiarybutyl ether
  • octyl nitrate e.g., octyl nitrate
  • xylene e.g., mineral spirits or kerosene
  • additives known to the art as described above and in the references there cited can be employed as the application calls for. Specifically, it is sometimes desirable to add one or more of corrosion inhibitors, cetane improvers, lubricity control agents, detergents, antigei compositions, and the like.
  • overt addition of water can be beneficial.
  • Overt addition of water e.g., from about 1 to about 65%, can be accomplished without rendering the platinum group metal catalyst compositions inactive.
  • fuel mixtures can be prepared as emulsions of diesel fuel and water, as mentioned above, but preferably including from about 5 to about 45% (more narrowly, 10 to 30%) water, for the purpose of controlling the amount of NO x produced during combustion.
  • emulsions can include a platinum group metal catalyst composition in a relative amount effective to provide the metal at a concentration of from about 0.1 to about 1.0 ppm, to reduce the carbon monoxide and hydrocarbon emissions, and employing a lipophilic emulsifier at a ratio of from about 1 :10,000 to about 1 :500,000 (more narrowly, from about 1 :50,000 to about 1 :250,000) based on the weight of the platinum group metal.
  • the droplets of lipophilic fluid as the internally-dispersed phase can comprise the fuel additive, including the platinum group metal and the water-functional composition, e.g., a suitable emulsifier having the capability to maintain an emulsion of this type.
  • the emulsifiers effective for the complex emulsions will preferably contain a hydrophilic emulsifier such as higher ethoxylated nonyl phenols, salts of alkyl and alkyl ether sulfates, ethoxylated nonyl phenols with higher degrees of ethoxyiation, higher polyethylene glycol mono- and di- esters, and higher ethoxylated sorbitan esters (e.g., higher in these contexts means from a lower levei of 4-6 to about 10 or more).
  • a hydrophilic emulsifier such as higher ethoxylated nonyl phenols, salts of alkyl and alkyl ether sulfates, ethoxylated nonyl phenols with higher degrees of ethoxyiation, higher polyethylene glycol mono- and di- esters, and higher ethoxylated sorbitan esters (e.g., higher in these contexts means from a lower
  • a fuel additive for use in preparing the complex emulsion preferably comprises a continuous hydrocarbon phase including a hydrophilic emulsifier at a concentration of from about 0.1 to about 10%, and a dispersed phase comprised of aqueous droplets having a platinum group metal catalyst composition dissolved or dispersed therein and a lipophilic emulsifier at a concentration of from about 0.1% to about 10% based on the weight of platinum group metal in the additive composition, said lipophilic emulsifier being charaterized by oil solubility and water dispersibility.
  • the lipophilic emulsifier is added to the oil to be used for the internal phase at a ratio of from about 0.1 to about 10% of the total composition.
  • Platinum group metal catalyst compositions may be dissolved or dispersed in this oil as desired.
  • the combined oii/iipophiiic emulsifier just described is added to a solution of the hydrophilic emulsifier in water with stirring to form an oil-in-water emulsion.
  • the concentration of hydrophilic emulsifier in the water is also between about 0.1 and 10% of the total composition.
  • Water- soluble or dispersible platinum group metal catalyst compositions may be dispersed in the water as needed.
  • step 2 The oil-in-water emulsion described in step 2 is then added to oil containing the lipophilic emulsifier at a ratio of 0.1 to 10% of the total composition to form the final oil/water-in-oil emulsion.
  • lipophilic emulsifiers suitable as the water-functional composition are, preferably, those emulsifiers having an HLB of less than about 10, and more preferably less than about 8.
  • HLB means "hydrophile- lipophile balance" and is determined, as known from the procedure developed by ICI Americas, Inc. of Wilmington, Delaware, from a test of the relative solubility or dispersibility of the emulsifier in water, with nondispersible being 1-4 and fully dispersible being 13.
  • the emulsifier can be anionic, nonionic or cationic.
  • anionic emulsifiers sodium or TEA petroleum sulfonates, sodium dioctyl sulfosuccinates, and ammonium or sodium isostearyol 2-lactyiates.
  • preferred cationic emulsifiers are lower ethoxylated amines, oleyl imidazoiines and other imidazoline derivatives.
  • nonionic emulsifiers are alkanolamides including oleamide, oleamide DEA, and other similar compounds, lower ethoxylated alkyl phenols, fatty amine oxides, and lower ethoxylated sorbitan esters (e.g., lower in these contexts means from 1 to an upper level of from about 4-6).
  • materials meeting the following criteria can be effective individually and in combinations to stabilize the presence of water- senstive and water-soluble platinum group metal catalyst compositions in water- containing systems.
  • Concentrations will be dependent on the exact formulation and the expected water content of the fuel, but concentrations of from about 0.01 to about 5%, based on the weight of the fuel as combusted, and assuming a water concentration of up to about 0.05%, are among those preferred. In some cases, it is more meaningful to express the concentration on the basis of the platinum group metal, and in this case it is preferably at a ratio of from about 10:1 to about 500,000:1 as compared to the weight of platinum group metal in the additive composition.
  • One exemplary combination of emulsifiers which can be utilized comprises about 25% to about 85% by weight of an amide, especially an alkanolamide or n-substituted alkyl amine; about 5% to about 25% by weight of a phenolic surfactant; and about 0% to about 40% by weight of a difunctional block polymer terminating in a primary hydroxyl group. More narrowly, the amide can comprise about 45% to about 65% of the emulsification system; the phenolic surfactant about, 5% to about 15%; and the difunctional block polymer, about 30% to about 40% of the emulsification system.
  • Suitable n-substituted alkyl amines and alkanolamides are those formed by the condensation of, respectively, an alkyl amine and an organic acid or a hydroxyalkyl amine and an organic acid, which is preferably of a length normally associated with fatty acids. They can be mono-, di-, or triethanolamines and include any one or more of the following: oleic diethanolamide (oleamide DEA), cocamide diethanolamine, lauramide DEA, polyoxyethylene (POE) cocamide, cocamide monoethanolamine (MEA), POE lauramide DEA, oleamide DEA, linoleamide DEA, stearamide MEA, and oleic triethanolamine, as well as mixtures thereof.
  • oleic diethanolamide oleamide DEA
  • cocamide diethanolamine lauramide DEA
  • POE polyoxyethylene
  • MEA cocamide monoethanolamine
  • POE lauramide DEA
  • alkanolamides are commercially available, including those under trade names such as Clindrol 100-0, from Clintwood Chemical Company of Chicago, Illinois; Schercomid ODA, from Scher Chemicals, Inc. of Clifton, New Jersey; Schercomid SO-A, also from Scher Chemicals, Inc.; Mazamide®, and the Mazamide series from PPG-Mazer Products Corp. of Gurnee, Illinois; the Mackamide series from Mclntyre Group, Inc. of University Park, Illinois; and the Witcamide series from Witco Chemical Co. of Houston, Texas.
  • the phenolic surfactant can be an ethoxylated alkyl phenol such as an ethoxylated nonylphenol or octylphenol.
  • ethylene oxide nonylphenol which is available commercially under the tradename Triton N from Union Carbide Corporation of Danbury, Connecticut and Igepal CO from Rhone-Poulenc Company of Wilmington, Delaware.
  • the block polymer which is an optional element of the emulsification system can comprise a nonionic, difunctional block polymer which terminates in a primary hydroxyl group and has a molecular weight ranging from about 1 ,000 to above about 15,000.
  • Such polymers are generally considered to be polyoxyalkylene derivatives of propylene glycol and are commercially available under the tradename Pluronic from BASF-Wyandotte Company of Wyandotte, New Jersey. Preferred among these poiymers are propylene oxide/ethyiene oxide block polymers commercially available as Pluronic 17R1.
  • the emulsification system should be present at a levei which will ensure effective emulsification of the water present, either alone or with a suitable lipophilic organic compound in which water is miscible (to be described in detail later).
  • the emulsification system can be present at a level of at least about 0.05% by weight of the fuel to do so.
  • the amount of the emulsification system which is present there is generally no need for more than about 5.0% by weight, nor, in fact, more than about 3.0% by weight.
  • a physical emulsion stabilizer in combination with the emulsification system noted above to maximize the stability of the emulsion.
  • Use of physical stabilizers also provides economic benefits due to their relatively low cost.
  • physical stabilizers increase emulsion stability by increasing the viscosity of immiscible phases such that separation of the oil/water interface is retarded.
  • suitable physical stabilizers are waxes, cellulose products, and gums such as whalen gum and xanthan gum.
  • the physical stabilizer is present in an amount of about 0.05% to about 5% by weight of the combination of chemical emulsifier and the physical stabilizer.
  • the resulting combination emulsifier/stabilizer can then be used at the same levels noted above for the use of the emulsification system.
  • the emulsifiers are preferably blended with the platinum group metal catalyst composition and the resulting blend is then admixed with the fuel and emulsified.
  • a suitable mechanical emulsifying apparatus such as an in-line emulsifying device, can be employed.
  • Preferred emulsion stabilities will be for time periods of from about 10 days at a minimum to about 1 month or more. More preferably, the emulsion will be stable for at least 3 months.
  • lipophilic organic compounds in which water is miscible will be water-miscible, fuel-soluble compounds such as butanol, butyl cellosolve (ethyleneglycol monobutyl ether), dipropylene-glycol monometyl ether, 2-hexyi hexanol, diacetone alcohol, hexylene glycol, and diisobutyl ketone.
  • fuel-soluble compounds such as butanol, butyl cellosolve (ethyleneglycol monobutyl ether), dipropylene-glycol monometyl ether, 2-hexyi hexanol, diacetone alcohol, hexylene glycol, and diisobutyl ketone.
  • materials meeting the following criteria can be effective: that they have a water miscibility of at least about 10 g of water per liter of the material, and be soluble in the fuel (when the material contains the 10 g of water) in an amount of about at least 10 g per liter of
  • the water functional composition will preferably be characterized by hydroxy, ketone, carboxylic acid funtionai group, ether linkage, amine group, or other polar functional groups that can serve as water acceptors on a hydrocarbon chain. Concentrations will be dependent on the exact formulation and the expected water content of the fuel, but concentrations of from about 0.01 to about 1.0%, based on the weight of the fuel as combusted, are among those preferred. In some cases, it is more meaningful to express the concentration on the basis of the platinum group metal, and in this case it is preferably at a ratio of from about 1,000:1 to about 500,000:1 relative the weight of platinum group metal in the additive composition.
  • 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.
  • platinum group metal salts such as chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, iron chloroplatinate, magnesium chloroplatinate, manganese chloroplatinate, and cerium chloroplatinate, as well as any of those compounds identified or included within the description set forth by Haney and Sullivan in U. S. Patent No. 4,629,472.
  • the platinum group metal catalyst compositions are effective to release catalytic platinum group metal in the combustion chamber, or when added to the exhaust gases, release the catalytic platinum group metal there.
  • the platinum group metal catalyst compositions can be employed with other catalytic metallic compositions utilized for improving economy, reducing emissions of pollutants such as hydrocarbons and carbon monoxide, and for improving the operation of particulate traps or oxidation catalysts.
  • useful metallic compositions are organometaUic salts of manganese, magnesium, calcium, iron, copper, cerium, sodium, lithium and potassium, which can be employed at suitable levels, e.g., from about 1 to about 100 ppm and preferably 20 to 60 ppm of the catalyst metal in combination with the platinum group metal catalyst in diesel fuels.
  • the alcoholates, sufonates, beta-diketonates and soaps e.g., selected from the group consisting of stearates, palmitates, laurates, tallates, napthanates, other fatty acid soaps, and mixtures of two or more of these, of copper, calcium, magnesium, manganese, iron, cerium, sodium, lithium and potassium compounds as are known as fuel soluble and useful fuel additives.
  • Some, such as set forth in the above citations are known as useful for reducing the temperature at which diesel traps can be regenerated.
  • the invention permits them to achieve their known function while the emissions of hydrocarbons and carbon monoxide are reduced.
  • the invention reduces the balance point sufficiently low to permit NO x reduction by modifying engine timing or exhaust gas recirculation without the concern for increased particulates which would normally be associated with those techniques.
  • lithium and sodium compounds are organometaUic compounds and complexes as well as the salts of lithium and sodium respectively, with suitable organic compounds such as alcohols or acids, e.g., aliphatic, alicyclic and aromatic alcohols and acids.
  • suitable organic compounds such as alcohols or acids, e.g., aliphatic, alicyclic and aromatic alcohols and acids.
  • exemplary of particular salts are the lithium and sodium salts of tertiary butyl alcohol and mixtures of these.
  • Other lithium and sodium organic salts are available and suitable for use to the extent that they are fuel-soluble and are stable in solution.
  • inorganic salts can also be employed to the extent that they can be efficiently dispersed in the fuel, such as in a stable emulsion or otherwise.
  • the specific lithium compounds are the lithium analogs of the above sodium compounds.
  • cerium Mi acetylacetonate cerium III napthenate
  • cerium octoate and other soaps such as stearate, neodecanoate, and octoate (2-ethylhexoate).
  • Ce (OOCR) 3 hydrocarbon, preferably C 2 to C 22 , and including aliphatic, alicyclic, aryl and alkylaryl.
  • copper acetylacetonate copper napthenate, copper tallate, and copper soaps of C 4 to C 22 fatty acids, including stearate, laurate, palmitate, octoate, neodecanoate and mixtures of any of these.
  • Fatty acids for these compounds can be derived from any animal or vegetable fat or oil, or fraction thereof, as well as from mineral oils.
  • These copper compounds are divalent compounds, with the soaps meeting the formula: Cu(OOCR) 2 .
  • 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) 5 ,iron napthenate, and iron tallate.
  • specific managanese compounds include methyicyclopentadienyl manganese tricarbonyl (CH 3 C 5 H 4 MN (CO) 3 , as described for example in U. S. Patent No. 4,191 ,536 to Niebylski; manganese acetylacetonate, ll and III valent; soaps including neodecanoate, stearate, tallate, napthenate and octoate.
  • the calcium and magnesium compounds can have the same anions as the copper compounds, but will also include a wider range of sulfonates and overbased sulfonates.
  • the catalyst compositions are preferably included in a fuel additive composition which will preferably include a solvent which is soluble in the fuel.
  • the fuel additive compositions may also contain other additives, such as detergents, antioxidants, and cetane improvers such as octyl nitrate which are known as beneficial to engine performance, but the use of such is not an essential feature of the invention.
  • solvent and other additives used will depend on the dosage of platinum group metal catalyst composition required and on what is a convenient concentration to handle relative to the amount of fuel to be treated. Typically, solvent (plus other like additive) volumes of about 0.1 to about 40.0 liters/gram of platinum are acceptable.
  • the fuel additive composition can be provided at a ratio so as to provide a sufficient level of platinum group catalyst metal in a relatively short period of time, i.e., under about 10 hours, more preferably under about 5 hours. Effective levels to do so can range up to about 30 ppm, more advantageously, about 15 to about 25 ppm. These levels should be provided for about 0.5 to about 10 hours. Maintenance amounts to intermittently or continuously provide from about 0.1 to about 1.0 ppm can then be provided, to maintain superior activ ⁇ ity. ln another alternative embodiment, an additive can be injected into the exhaust system, preferably just prior to the particulate trap, to supply catalyst on an initial or renewal basis either continuously or intermittently.
  • the additive can contain platinum group metal alone or in combination with an auxiliary catalyst metal.
  • concentration of catalyst for this use will depend on the dosage and the desired effect. In one embodiment the concentration can be sufficient to supply from 1 to 100 ppm for the platinum group metal and from 100 to 10,000 ppm for the auxiliary catalyst metals.
  • the solvent or carrier should be rapidly volatilized and any organic component of the solvent or the catalyst compounds should be capable of burning off at the steady state exhaust temperature, e.g. in the range of 300° to 600° F.
  • Exemplary solvents or carriers include water, alcohols, hydrocarbons, and other suitable organic liquids. The organic liquids can be of benefit in NO x reduction.
  • platinum group metal catalyst compositions reduces the usual conversion of SO 2 to SO 3 as compared to conventional platinum-catalyzed particulate traps which have the platinum metal applied.
  • platinum group metal catalyst functions in the trap to rapidly burn the carbon with a minimal requirement for oxygen to produce reducing conditions in the trap in so far as the oxidation of sulfur compounds is concerned.
  • This selectivity does not diminish the ability of the catalyst to reduce the emissions of carbon monoxide and unburned hydrocarbons on a steady basis.
  • the use of the noted catalyst metals when effective catalyst levels are built up, can reduce the balance point such that the particulates trapped in the particulate trap are removed at the same rate they are trapped whereby self-regeneration of the particulate trap, especially in a four-cycle diesel engine, may occur and at temperatures lower than would occur without use of the catalysts of the invention. Even if self-regeneration cannot completely occur, i.e., in a four-cycle engine which is not operating hot enough or in a two-cycle engine, the use of the described additives can reduce the temperature to which an auxiliary heat source is required to raise the diesel engine particulate trap, thereby increasing the efficiency of the use of the auxiliary heat source. In this way, further significant improvements in the use of a diesel engine particulate trap are obtained, without the art accepted tradeoff of substantially increased back pressure caused by clogging of the trap by collected particulates.
  • Peak Power 230 kW at 2100 rev/min Peak Torque (Measured) 1210 Nm at 1500 rev/min Idle Speed 625-725 rev/min Bore 125 mm Stroke 136 mm
  • Fuel and oil with low haiide contents were employed.
  • the fuel used was
  • the fuel halide content was 3 ppm.
  • the oil used was Amoco Premier II SAE 15W-40, analyzed as containing 27.5 ppm Chloride.
  • the platinum group metal catalyst composition had the following composition and was mixed with the fuel at a dosage rate of 1 :2600 by volume (0.15 ppm, Pt):
  • blank additive (identical except that there is no platinum component) was mixed at the same rate.
  • the mixed fuel was supplied to the test cell in palletted containers with a continuous recirculation system to ensure the additive stayed thoroughly mixed.
  • the engine test schedule was designed to provide baseline data, a period of conditioning with the additive and a repeat of tests after the conditioning: Phase 1 was designed to give a reliable baseline on fuel doped with blank additive; and
  • the fuel was doped with platinum-based additive and 250 hours accumulated prior to repeating the baseline tests.
  • a duty cycle consisting of eight steps and six different conditions was designed to provide a mix of real-life operating conditions and to allow Ioading-up of the trap and regeneration.
  • measurements of temperatures, pressures, fuel consumption and gaseous emissions were made at approximately ten-hourly intervals at three keypoints:
  • the platinum additive and trap combination is able to achieve large HC and CO emissions without causing significant particulate increases from sulfate generation, even at high loads and temperatures.
  • the platinum additive effectively creates and continually renews a very large lightly loaded catalyst in the engine, exhaust and trap.
  • the equivalent may be difficult to achieve by conventional means due to space limitations, problems with long-term stability with very low platinum loadings, and masking of the catalyst material by carbon deposits.
  • the addition of platinum additive will provide catalyst type benefits from reducing odor, etc., without any penalties from sulphate generation.
  • the additive used in combination with a trap as described above has been compared with uncatalyzed fuels, both through-flow catalysts and catalyzed trap systems.
  • the objective of through-flow catalysts on diesel engines is to reduce carbon monoxide, hydrocarbon emissions and burn the soluble organic fraction of particulates, preferably without forming sulfates from the sulfur in the fuel.
  • the benefits of through-flow catalyst are the reduction of heavy hydrocarbons (fuel and oil) in the particulate. There is also a benefit from the reduction of gaseous hydrocarbons by the reduction of odor, etc.
  • the HC conversion efficiency ( Figure 5) for the platinum additive and trap combination is as high as the most active catalyst A but the sulfur conversion efficiency (Figure 6) is much lower and stays below 1 % up to 670°C.
  • Figure 7 shows the same data as a trade-off between sulfur and HC conversion. In this figure the optimum is to have a system which operates in the bottom right hand corner, maximizing HC conversion with little sulfur conversion (sulfate generation) penalty on particulates.
  • the platinum additive and trap combination is clearly excellent in this respect.
  • a test has been carried out to assess the effect of a diesel fuel to which is added a platinum group metal catalyst composition and compare that to baseline with no aditive and to a diesel fuel containing a fuel soluble auxiliary catalyst metal composition containing copper on the performance and emissions of a heavy duty diesel engine fitted with a non-catalyzed particulate trap.
  • the platinum group metal catalyst composition is added with a fuel additive having the formulation of the Example 1 and was mixed with the fuel at a dosage rate of 1 :1560 by volume (0.25 ppm, Pt).
  • the copper compound was present in the fuel at a level to give a dosage of 30 ppm copper in the fuel.
  • the effect of the additives on particulate trap regeneration characteristics was also evaluated.
  • the platinum additive gave a slight improvement in average engine out (15%) and consequently after trap (19%) particulate emissions.
  • the platinum additive reduced the particulate trap balance point temperature by 59°C to 471 °C.
  • the balance point temperature for platinum plus copper treatment was 273 °C (257 °C lower than the baseline).
  • the additives gave several tangible benefits with no discernible adverse affects on regulated emissions.
  • the effect of the platinum plus copper additive on trap regeneration characteristics offers an attractive solution to the traditional problems of non-catalyzed wall flow particulate traps.
  • Another diesel fuel additive containing a platinum group metal catalyst composition has the following formulation and is mixed with the fuel at a dosage rate of 1 :400 by volume (0.09 ppm Pt and 0.07 ppm Pd):
  • Another diesel fuel additive containing a platinum group metal catalyst composition has the following formulation and is mixed with the fuel at a dosage rate of 1 :400 by volume (0.15 ppm Pd).
  • Example 3 The procedures of Example 3 were repeated, but this time adding to the beginning of the test procedure a conditioning procedure wherein the platinum fuel additive composition was employed at a concentration giving 0.50 ppm platinum metal in the fuel. The conditioning period was run for 50 hours after a new trap was fitted. Hydrocarbon emissions (less than 10 ppm) and carbon monoxide (less than 0.005 %) were considered extremely low. The balance point at this time was found to between 475 and 500 °C.
  • test fuel was then changed to one containing 0.25 ppm platinum and the hydrocarbon emissions and carbon monoxide were found to increase slightly and the balance point remained between 475 and 500 °C.
  • test fuel was then changed to one containing 0.25 ppm platinum and 30 ppm copper. Following a conditioning period of 8 hours, the balance point was found to be between 350 and 375 °C.
  • test fuel was again changed to the 0.25 ppm platinum additive alone and the balance point was again determined after overnight operation and found to be between 475 and 500 °C.
  • Example 3 The procedures of Example 3 were again repeated, but this time using a cerium compound (Rhone Poulenc DP-06, cerium fatty acid soap) in place of the copper additive and adding to the beginning of the test procedure a conditioning procedure wherein the platinum fuel additive composition was employed at a concentration giving 0.50 ppm platinum metal in the fuel.
  • a cerium compound Rhone Poulenc DP-06, cerium fatty acid soap
  • Example 3 Baseline data with no additve was not retaken, given the similar set up to that of Example 3 (the same engine and a similar, although not identical, trap).
  • the conditioning period with 0.50 ppm platinum was run for 50 hours after the new trap was fitted. Emissions of NO x , unburned hydrocarbons, carbon monoxide and particulates were monitored.
  • the test fuel was then changed to one containing 0.25 ppm platinum and the engine was conditioned for another eight hours.
  • test fuel was then changed to one containing 0.25 ppm platinum and 30 ppm cerium. Following a conditioning period of 8 hours, the emissions of NO x , unburned hydrocarbons, carbon monoxide and particulates were monitored. The results are presented in the foilowing Table 2.
  • test fuel was again supplied with the 0.25 ppm platinum * and 30 ppm of the cerium, and the balance point was determined to be between 425 and 450°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Catalysts (AREA)

Abstract

Les procédés de l'invention permettent de réduire les émissions toxiques des moteurs Diesel en utilisant une combinaison de dispositifs mécaniques et d'additifs de carburant. Dans un mode de réalisation, on parvient à diminuer les émissions Diesel d'oxyde azoté (Nox) et de matières particulaires, en même temps que les gaz d'hydrocarbures et le monoxyde de carbone, en associant le recyclage des gaz d'échappement et la modification du système de distribution à un piège de matières particulaires et une composition de catalyseur métallique du groupe des platines. Dans un autre mode de réalisation, on emploie une composition de catalyseur polymétallique, comprenant l'association d'une composition de catalyseur métallique du groupe des platines et d'au moins une composition auxiliaire de métal catalyseur, notamment le cérium ou le cuivre, pour fournir du métal catalyseur au système d'échappement constitué d'un piège Diesel et pour abaisser le point d'équilibre du piège de matières particulaires (température à laquelle la vitesse de remplissage du piège est égale à la vitesse de régénération) tout en diminuant également les émissions de monoxyde de carbone et d'hydrocarbures non brûlés. Les données destinées aux catalyseurs de platine, de cuivre et de cérium permettent de fixer les doses utiles. Des expériences mettent également en évidence le maintien sélectif de la faible oxydation de SO2 en SO3.
PCT/US1996/011908 1995-07-18 1996-07-18 Procedes permettant de diminuer les emissions toxiques d'un moteur diesel WO1997004045A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96925366A EP0854903A4 (fr) 1995-07-18 1996-07-18 Procedes permettant de diminuer les emissions toxiques d'un moteur diesel
AU65489/96A AU6548996A (en) 1995-07-18 1996-07-18 Methods for reducing harmful emissions from a diesel engine
MXPA/A/1998/000511A MXPA98000511A (en) 1995-07-18 1998-01-16 Method to reduce harmful emissions caused by die engines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US50390995A 1995-07-18 1995-07-18
US08/503,909 1995-07-18
US08/514,978 1995-08-14
US08/514,978 US6003303A (en) 1993-01-11 1995-08-14 Methods for reducing harmful emissions from a diesel engine

Publications (1)

Publication Number Publication Date
WO1997004045A1 true WO1997004045A1 (fr) 1997-02-06

Family

ID=27054661

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/011908 WO1997004045A1 (fr) 1995-07-18 1996-07-18 Procedes permettant de diminuer les emissions toxiques d'un moteur diesel

Country Status (4)

Country Link
EP (1) EP0854903A4 (fr)
AU (1) AU6548996A (fr)
CA (1) CA2227141A1 (fr)
WO (1) WO1997004045A1 (fr)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6023928A (en) * 1997-04-17 2000-02-15 Clean Diesel Technologies, Inc. Method for reducing emissions from a diesel engine
WO2000030739A1 (fr) * 1998-11-24 2000-06-02 Clean Diesel Technologies, Inc. Comburant particulaire catalyse servant a reduire les emissions particulaires d'un moteur diesel et procede associe
WO2000058422A1 (fr) * 1999-03-26 2000-10-05 Infineum International Limited Compositions de fuel-oil
WO2002012417A1 (fr) * 2000-08-03 2002-02-14 Cesare Pedrazzini Additif utilise pour reduire la formation de particules dans des emissions provenant de la combustion du diesel
EP1277827A1 (fr) * 2001-07-11 2003-01-22 SFA International, Inc. Méthode de réduction de fumée et de particules émises lors du fonctionnement avec des combustibles pétroliers liquides, de moteurs alternatifs à allumage par compression
EP1344813A1 (fr) * 2002-03-13 2003-09-17 Infineum International Limited Compositions d'additifs pour combustible pour moteur diesel équipé d'un piège à particules
EP1344812A1 (fr) * 2002-03-13 2003-09-17 Infineum International Limited Compositions additives de sel métallique surbasique pour combustible diesel pour l'amélioration de pièges à particules
WO2003040270A3 (fr) * 2001-11-06 2003-12-04 Oxonica Ltd Nanoparticules d'oxyde de cerium
EP1409617A1 (fr) * 2000-05-08 2004-04-21 Clean Diesel Technologies Inc. Carburant diesel a faibles emissions
EP1411108A1 (fr) * 2002-10-16 2004-04-21 Ethyl Corporation Proédé d'amélioration de l'opération d'un sytème de post-traitement de combustion de diésel.
EP1411106A1 (fr) * 2002-10-16 2004-04-21 Ethyl Corporation Procédé d'oxydation de la suie et de réduction de l'accumulation de suie dans un appareil de post-traitement de combustion de diésel.
EP1478885A1 (fr) * 2002-02-04 2004-11-24 Clean Diesel Technologies Inc. Combustion a emissions reduites utilisant des catalyseurs de combustion metallique multicomposants
US8147566B2 (en) 1999-11-23 2012-04-03 Krogh James A Fuel additive, additive-containing fuel compositions and method of manufacture
US8211190B2 (en) 1999-03-26 2012-07-03 Infineum International Limited Fuel oil compositions
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
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
US9511358B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. Spinel compositions and applications thereof
US9545626B2 (en) 2013-07-12 2017-01-17 Clean Diesel Technologies, Inc. Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate
US9555400B2 (en) 2013-11-26 2017-01-31 Clean Diesel Technologies, Inc. Synergized PGM catalyst systems including platinum for TWC application
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
US9771534B2 (en) 2013-06-06 2017-09-26 Clean Diesel Technologies, Inc. (Cdti) Diesel exhaust treatment systems and methods
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters
US10533472B2 (en) 2016-05-12 2020-01-14 Cdti Advanced Materials, Inc. Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4568357A (en) * 1984-12-24 1986-02-04 General Motors Corporation Diesel fuel comprising cerium and manganese additives for improved trap regenerability
US4629472A (en) * 1985-06-19 1986-12-16 Fuel Tech, Inc. Method and apparatus for improving combustion, thermal efficiency and reducing emissions by treating fuel
US4664677A (en) * 1983-10-05 1987-05-12 The Lubrizol Corporation Manganese and copper containing compositions
US4892562A (en) * 1984-12-04 1990-01-09 Fuel Tech, Inc. Diesel fuel additives and diesel fuels containing soluble platinum group metal compounds and use in diesel engines
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines
US5215652A (en) * 1984-12-04 1993-06-01 Platinum Plus, Inc. Method for regenerating, replacing or treating the catalyst in a hydroprocessing reactor
US5266083A (en) * 1988-12-28 1993-11-30 Platinum Plus, Inc. Method for reducing pollution emissions from a diesel engine
US5279627A (en) * 1992-11-06 1994-01-18 The Lubrizol Corporation Copper-containing aromatic mannich complexes and concentrates and diesel fuels containing same
US5322671A (en) * 1992-02-25 1994-06-21 Blue Planet Technologies Co., L.P. Catalytic vessel
US5360459A (en) * 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5376154A (en) * 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
US5387569A (en) * 1992-02-25 1995-02-07 Blue Planet Technologies Co., L.P. Catalytic solution suitable for converting combustion emissions
US5386690A (en) * 1992-02-25 1995-02-07 Blue Planet Technologies Co., L.P. Catalytic system
US5501714A (en) * 1988-12-28 1996-03-26 Platinum Plus, Inc. Operation of diesel engines with reduced particulate emission by utilization of platinum group metal fuel additive and pass-through catalytic oxidizer
US5535708A (en) * 1993-08-30 1996-07-16 Platinum Plus, Inc. Reduction of nitrogen oxides emissions from diesel engines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3336893A (en) * 1991-12-16 1993-07-19 Platinum Plus, Inc. Method for reducing particulate emissions from a diesel engine with organometallic platinum group metal coordination composition
ES2152300T3 (es) * 1992-11-10 2001-02-01 Clean Diesel Tech Inc Metodo para reducir las emisiones nocivas de un motor diesel equipado con una trampa para particulas.
EP0708809B1 (fr) * 1993-07-12 2000-09-20 Clean Diesel Technologies, Inc. PROCEDE DE REDUCTION DES EMISSIONS DE NOx ET DES MATIERES PARTICULAIRES REJETEES PAR UN MOTEUR DIESEL

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664677A (en) * 1983-10-05 1987-05-12 The Lubrizol Corporation Manganese and copper containing compositions
US4892562A (en) * 1984-12-04 1990-01-09 Fuel Tech, Inc. Diesel fuel additives and diesel fuels containing soluble platinum group metal compounds and use in diesel engines
US5215652A (en) * 1984-12-04 1993-06-01 Platinum Plus, Inc. Method for regenerating, replacing or treating the catalyst in a hydroprocessing reactor
US4568357A (en) * 1984-12-24 1986-02-04 General Motors Corporation Diesel fuel comprising cerium and manganese additives for improved trap regenerability
US4629472A (en) * 1985-06-19 1986-12-16 Fuel Tech, Inc. Method and apparatus for improving combustion, thermal efficiency and reducing emissions by treating fuel
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines
US5266083A (en) * 1988-12-28 1993-11-30 Platinum Plus, Inc. Method for reducing pollution emissions from a diesel engine
US5501714A (en) * 1988-12-28 1996-03-26 Platinum Plus, Inc. Operation of diesel engines with reduced particulate emission by utilization of platinum group metal fuel additive and pass-through catalytic oxidizer
US5360459A (en) * 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5376154A (en) * 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
US5322671A (en) * 1992-02-25 1994-06-21 Blue Planet Technologies Co., L.P. Catalytic vessel
US5387569A (en) * 1992-02-25 1995-02-07 Blue Planet Technologies Co., L.P. Catalytic solution suitable for converting combustion emissions
US5386690A (en) * 1992-02-25 1995-02-07 Blue Planet Technologies Co., L.P. Catalytic system
US5348559A (en) * 1992-11-06 1994-09-20 The Lubrizol Corporation Copper-containing aromatic mannich complexes and concentrates and diesel fuels containing same
US5279627A (en) * 1992-11-06 1994-01-18 The Lubrizol Corporation Copper-containing aromatic mannich complexes and concentrates and diesel fuels containing same
US5535708A (en) * 1993-08-30 1996-07-16 Platinum Plus, Inc. Reduction of nitrogen oxides emissions from diesel engines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0854903A4 *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6023928A (en) * 1997-04-17 2000-02-15 Clean Diesel Technologies, Inc. Method for reducing emissions from a diesel engine
CN100351502C (zh) * 1997-04-17 2007-11-28 克林迪塞尔技术公司 降低柴油机排出物的方法
WO2000030739A1 (fr) * 1998-11-24 2000-06-02 Clean Diesel Technologies, Inc. Comburant particulaire catalyse servant a reduire les emissions particulaires d'un moteur diesel et procede associe
WO2000058422A1 (fr) * 1999-03-26 2000-10-05 Infineum International Limited Compositions de fuel-oil
US8211190B2 (en) 1999-03-26 2012-07-03 Infineum International Limited Fuel oil compositions
US8147566B2 (en) 1999-11-23 2012-04-03 Krogh James A Fuel additive, additive-containing fuel compositions and method of manufacture
EP1409617A4 (fr) * 2000-05-08 2004-04-21 Clean Diesel Tech Inc Carburant diesel a faibles emissions
EP1409617A1 (fr) * 2000-05-08 2004-04-21 Clean Diesel Technologies Inc. Carburant diesel a faibles emissions
WO2002012417A1 (fr) * 2000-08-03 2002-02-14 Cesare Pedrazzini Additif utilise pour reduire la formation de particules dans des emissions provenant de la combustion du diesel
US7524338B2 (en) 2000-08-03 2009-04-28 Cesare Pedrazzini Additive for reducing particulate in emissions deriving from the combustion of diesel oil or fuel oil having a metallic oxidation catalyst, at least one organic nitrate, and a dispersing agent
EP1277827A1 (fr) * 2001-07-11 2003-01-22 SFA International, Inc. Méthode de réduction de fumée et de particules émises lors du fonctionnement avec des combustibles pétroliers liquides, de moteurs alternatifs à allumage par compression
WO2003006587A1 (fr) * 2001-07-11 2003-01-23 Sfa International, Inc. Procede destine a reduire les emissions de fumee et de particules dans des moteurs alternatifs a combustion par compression fonctionnant avec du carburant a base de petrole liquide
WO2003040270A3 (fr) * 2001-11-06 2003-12-04 Oxonica Ltd Nanoparticules d'oxyde de cerium
US7169196B2 (en) 2001-11-06 2007-01-30 Oxonica Materials Limited Fuel or fuel additive containing doped cerium oxide nanoparticles
EP1478885A1 (fr) * 2002-02-04 2004-11-24 Clean Diesel Technologies Inc. Combustion a emissions reduites utilisant des catalyseurs de combustion metallique multicomposants
EP1478885A4 (fr) * 2002-02-04 2010-05-19 Clean Diesel Tech Inc Combustion a emissions reduites utilisant des catalyseurs de combustion metallique multicomposants
EP1344810A1 (fr) * 2002-03-13 2003-09-17 Infineum International Limited Compositions d'additifs pour combustible pour moteur diesel équipé d'un piège à particules
US7585336B2 (en) 2002-03-13 2009-09-08 Infineum International Limited Fuel additive compositions for diesel engine equipped with a particulate trap
EP1344812A1 (fr) * 2002-03-13 2003-09-17 Infineum International Limited Compositions additives de sel métallique surbasique pour combustible diesel pour l'amélioration de pièges à particules
EP1344813A1 (fr) * 2002-03-13 2003-09-17 Infineum International Limited Compositions d'additifs pour combustible pour moteur diesel équipé d'un piège à particules
EP1411106A1 (fr) * 2002-10-16 2004-04-21 Ethyl Corporation Procédé d'oxydation de la suie et de réduction de l'accumulation de suie dans un appareil de post-traitement de combustion de diésel.
SG126731A1 (en) * 2002-10-16 2006-11-29 Afton Chemical Intangibles Llc Method of oxidizing soot and reducing soot accumulation in a diesel fuel combustion after treatment system
EP1411108A1 (fr) * 2002-10-16 2004-04-21 Ethyl Corporation Proédé d'amélioration de l'opération d'un sytème de post-traitement de combustion de diésel.
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
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
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
US9475005B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Three-way catalyst systems including Fe-activated Rh and Ba-Pd material compositions
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
US10533472B2 (en) 2016-05-12 2020-01-14 Cdti Advanced Materials, Inc. Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters

Also Published As

Publication number Publication date
EP0854903A1 (fr) 1998-07-29
CA2227141A1 (fr) 1997-02-06
EP0854903A4 (fr) 1999-04-21
MX9800511A (es) 1998-05-31
AU6548996A (en) 1997-02-18

Similar Documents

Publication Publication Date Title
US6003303A (en) Methods for reducing harmful emissions from a diesel engine
US5501714A (en) Operation of diesel engines with reduced particulate emission by utilization of platinum group metal fuel additive and pass-through catalytic oxidizer
WO1997004045A1 (fr) Procedes permettant de diminuer les emissions toxiques d'un moteur diesel
EP0668899B1 (fr) Procede de reduction des emissions nocives d'un moteur diesel equipe d'un piege a particules
EP0708809B1 (fr) PROCEDE DE REDUCTION DES EMISSIONS DE NOx ET DES MATIERES PARTICULAIRES REJETEES PAR UN MOTEUR DIESEL
US6051040A (en) Method for reducing emissions of NOx and particulates from a diesel engine
EP0802960B1 (fr) Composition pour diesel comprenant un additif a base de metaux du groupe du platine, pour carburants contenant de l'eau.
EP1009922B1 (fr) Procede de reduction des emissions d'un moteur diesel
US8006652B2 (en) Emissions control system for diesel fuel combustion after treatment system
WO1997028358A1 (fr) Methode et dispositif de reduction des emissions nocives d'un moteur diesel par injection d'un catalyseur de post combustion
WO1997009523A1 (fr) Procedes d'amelioration du fonctionnement d'un moteur a catalyseur
CA2438157C (fr) Methode d'oxydation de la suie et de reduction de l'accumulation de suie dans un systeme de combustion de carburant diesel a post-traitement
EP1411108A1 (fr) Proédé d'amélioration de l'opération d'un sytème de post-traitement de combustion de diésel.
KR19990029096A (ko) 디젤엔진으로부터의 유해 배출물을 감소시키는 방법
MXPA98000511A (en) Method to reduce harmful emissions caused by die engines

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2227141

Country of ref document: CA

Kind code of ref document: A

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PA/a/1998/000511

Country of ref document: MX

Ref document number: 1019980700400

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1996925366

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1996925366

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019980700400

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1019980700400

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1996925366

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996925366

Country of ref document: EP