US20010001354A1 - Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter - Google Patents

Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter Download PDF

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Publication number
US20010001354A1
US20010001354A1 US09/756,383 US75638301A US2001001354A1 US 20010001354 A1 US20010001354 A1 US 20010001354A1 US 75638301 A US75638301 A US 75638301A US 2001001354 A1 US2001001354 A1 US 2001001354A1
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United States
Prior art keywords
platinum
rhodium
composition according
gasoline
compounds
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Abandoned
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US09/756,383
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English (en)
Inventor
Jeremy Peter-Hoblyn
James Valentine
Barry Sprague
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Individual
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Individual
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Priority to US09/756,383 priority Critical patent/US20010001354A1/en
Publication of US20010001354A1 publication Critical patent/US20010001354A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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
    • 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
    • C10L1/14—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
    • C10L1/18—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
    • C10L1/30—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)

Definitions

  • the invention relates to compositions and methods that enable reduction of emissions while permitting a gasoline engine to operate efficiently.
  • Catalytic converters are standard on gasoline-powered automobiles in countries where regulators are aggressively attempting to control air quality. Many attempts have been made to balance their cost and effectiveness over reasonable periods of operation and the determination of effective catalyst compositions has progressed to the point that it is generally understood that combinations of platinum, palladium and rhodium are required. The procedures for catalyzing new catalytic converters are also fairly well worked out. In addition, several attempts have been made to renew them during operation. To this end several gasoline additives have been mentioned.
  • the metal compounds have polar metal-ligand bonds, preferably formed by purely inorganic ligands such as halogens, oxygen, etc.
  • the preferred compounds of platinum “are alkali salts of platinum hydrochloric acid X 2 PtCl 6 , where X is” potassium, rubidium or cesium.
  • Applicants have determined, however, that the chlorides have several disadvantages, among which are a corrosive effect on the exhaust system, including certain catalyst supports, and a tendency to release catalyst metals from a catalyst support due to a decrease in the vapor pressure of the metal compounds.
  • chlorides can present negative health and safety issues.
  • the concept of modulating concentration by varying the surface contact appears problematic in view of an expected variation of solubility with temperature and fuel composition.
  • the composition of the invention comprises a blend of rhodium acetylacetonate and a fuel-soluble organo-platinum compound, preferably one selected from the group consisting of platinum acetylacetonate and compounds having the general formula XPtR 1 R 2 wherein X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R 1 and R 2 are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10 carbons, e.g., diphenyl cyclooctadiene platinum(II).
  • the process of the invention comprises operating a gasoline engine equipped with a three-way catalytic converter by combusting gasoline containing a rhodium- and platinum-containing composition as defined above.
  • FIGURE is a graphical presentation of the results of engine tests run with the gasoline additive of the invention.
  • the invention relates to gasoline engines equipped with three-way catalytic converters.
  • This type of catalyst has become standard in the United States and many other countries for reducing the emissions of gaseous hydrocarbons, carbon monoxide and NO x . They typically have functions effective for both chemical reduction of the NO x and chemical oxidation of the hydrocarbons and carbon monoxide. They are required by various regulatory bodies to meet specific standards. Those numerical limits are not intended to limit the definition of the “three-way catalytic converter” as set forth above.
  • Gasoline is defined herein to have its usual meaning and to include those fuels defined as such by the ASTM and European standards and is intended to include all fuels capable of operating an engine of the Otto type.
  • these will be hydrocarbon fuels which are characterized as having a boiling point within the gasoline fraction range, e.g., from 90 to 220° F., and will typically contain additives to increase the oxygen content, improve octane and maintain the engine free of deposits that would tend to decrease engine performance.
  • Gasoline engines equipped with three-way catalysts emit less NO x hydrocarbons and carbon monoxide when operated on fuels containing a bimetallic catalyst comprising rhodium acetylacetonate and a fuel-soluble platinum compound such as diphenyl cyclooctadiene platinum(II) or platinum acetyl acetonate.
  • the total metals in the additive will be dosed at a concentration of less than about 2 ppm (e.g., 0.01 to 2 ppm based on the weight of metal in milligrams to volume of fuel in liters). Higher doses, e.g., up to about 10 ppm can be employed for shock treatments.
  • the additives will contain the appropriate concentrations of the metal compounds to give the appropriate dosage based on the amount of gasoline burned in the engine. Preferred dosages will be from about 0.15 to about 1.5 ppm, with a ratio of platinum to rhodium of from about 3:1 to about 15:1.
  • the compositions of the invention will preferably include a gasoline-miscible solvent such as mineral spirits, toluene and isopropyl alcohol.
  • platinum compounds are, in addition to platinum acetylacetonate, those having the general formula XPtR 1 R 2 wherein X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R 1 and R 2 are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10.
  • X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration and R 1 and R 2 are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10.
  • the preparation of the ligand-containing materials identified above is set out in the above patents to Bowers, et al., and Epperly, et al. The disclosures of these patents are incorporated herein by reference.
  • a gasoline engine is fed a gasoline composition including the bimetallic catalyst composition of the invention.
  • the gasoline is combusted in a combustion chamber of the engine and the organic portions of the rhodium and platinum compounds are oxidized, thereby releasing the rhodium and platinum as active catalyst species in exhaust gases generated by the combustion.
  • the resulting exhaust gases are then passed through the catalytic converter whereby rhodium and platinum are deposited in the catalytic converter in active form.
  • Rhodium acetylacetonate is a commercially available material, and is unexpectedly effective when used in combination with a fuel-soluble platinum compound in the composition and method of the invention.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
US09/756,383 1997-01-31 2001-01-08 Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter Abandoned US20010001354A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/756,383 US20010001354A1 (en) 1997-01-31 2001-01-08 Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79229797A 1997-01-31 1997-01-31
US09/756,383 US20010001354A1 (en) 1997-01-31 2001-01-08 Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter

Related Parent Applications (1)

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US79229797A Continuation 1997-01-31 1997-01-31

Publications (1)

Publication Number Publication Date
US20010001354A1 true US20010001354A1 (en) 2001-05-24

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US09/756,383 Abandoned US20010001354A1 (en) 1997-01-31 2001-01-08 Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter

Country Status (7)

Country Link
US (1) US20010001354A1 (de)
EP (1) EP0970165B1 (de)
AT (1) ATE283333T1 (de)
DE (1) DE69827778T2 (de)
ES (1) ES2232936T3 (de)
TW (1) TW499475B (de)
WO (1) WO1998033871A1 (de)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050081430A1 (en) * 2001-11-09 2005-04-21 Carroll Robert W. Method and composition for improving fuel combustion
US20080318765A1 (en) * 2007-06-19 2008-12-25 Aradi Allen A Nanoalloys in emissions control after-treatment systems
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
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
US9737239B2 (en) 2011-10-17 2017-08-22 Atlas5D, Inc. Systems and methods for tracking body surfaces of individuals
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
US10013756B2 (en) 2015-03-13 2018-07-03 Atlas5D, Inc. Methods and systems for measuring use of an assistive device for ambulation
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4891050A (en) * 1985-11-08 1990-01-02 Fuel Tech, Inc. Gasoline additives and gasoline containing soluble platinum group metal compounds and use in internal combustion engines
US5034020A (en) * 1988-12-28 1991-07-23 Platinum Plus, Inc. Method for catalyzing fuel for powering internal combustion engines

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7503944B2 (en) 2001-11-09 2009-03-17 Carroll Robert W Method and composition for improving fuel combustion
US20090282730A1 (en) * 2001-11-09 2009-11-19 Robert Wilfred Carroll Method and composition for improving fuel combustion
US8287607B2 (en) 2001-11-09 2012-10-16 Robert Wilfred Carroll Method and composition for improving fuel combustion
US8945244B2 (en) 2001-11-09 2015-02-03 Robert W. Carroll Method and composition for improving fuel combustion
US20050081430A1 (en) * 2001-11-09 2005-04-21 Carroll Robert W. Method and composition for improving fuel combustion
US20080318765A1 (en) * 2007-06-19 2008-12-25 Aradi Allen A Nanoalloys in emissions control after-treatment systems
US9737239B2 (en) 2011-10-17 2017-08-22 Atlas5D, Inc. Systems and methods for tracking body surfaces of individuals
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
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
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US10013756B2 (en) 2015-03-13 2018-07-03 Atlas5D, Inc. Methods and systems for measuring use of an assistive device for ambulation
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
WO1998033871A1 (en) 1998-08-06
DE69827778T2 (de) 2005-11-10
EP0970165A4 (de) 2001-01-24
EP0970165A1 (de) 2000-01-12
DE69827778D1 (de) 2004-12-30
ATE283333T1 (de) 2004-12-15
TW499475B (en) 2002-08-21
ES2232936T3 (es) 2005-06-01
EP0970165B1 (de) 2004-11-24

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