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EP0970165B1 - Verfahren zur verminderung von emissionen eines mit einem dreiwegekatalysator ausgerüsteten benzinmotors - Google Patents

Verfahren zur verminderung von emissionen eines mit einem dreiwegekatalysator ausgerüsteten benzinmotors Download PDF

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Publication number
EP0970165B1
EP0970165B1 EP98908457A EP98908457A EP0970165B1 EP 0970165 B1 EP0970165 B1 EP 0970165B1 EP 98908457 A EP98908457 A EP 98908457A EP 98908457 A EP98908457 A EP 98908457A EP 0970165 B1 EP0970165 B1 EP 0970165B1
Authority
EP
European Patent Office
Prior art keywords
platinum
rhodium
gasoline
catalytic converter
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98908457A
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English (en)
French (fr)
Other versions
EP0970165A1 (de
EP0970165A4 (de
Inventor
Jeremy D. Peter-Hoblyn
James M. Valentine
Barry N. Sprague
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clean Diesel Technologies Inc
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Clean Diesel Technologies Inc
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Filing date
Publication date
Application filed by Clean Diesel Technologies Inc filed Critical Clean Diesel Technologies Inc
Publication of EP0970165A1 publication Critical patent/EP0970165A1/de
Publication of EP0970165A4 publication Critical patent/EP0970165A4/de
Application granted granted Critical
Publication of EP0970165B1 publication Critical patent/EP0970165B1/de
Anticipated expiration legal-status Critical
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 methods that enable reduction of emissions while permitting a gasoline engine to operate efficiently.
  • the art has endeavored to provide an additive for gasoline, which could be used for an entire fleet to maintain a suitable level of catalyst activity. It has further looked for a specific additive that could be added to gasoline at a suitable dosage to renew the activity of a catalytic converter that has lost vigor.
  • This search has been difficult because effectiveness for one purpose must be balanced with other factors such as chemical composition necessary to deliver the catalyst to the catalytic converter at a cost that is practical and safe in terms of toxicity and handling. This cost has been found to be a matter of initial synthesis as well as to the presence of incompatible chemical species. Other factors that need to be balanced include the requirement that the added chemical compositions not damage or alter in a negative way components and functions of the engine and its emission control system.
  • the search for effective catalytic fuel additives for improving the operation of a catalytic converter is a difficult technical problem because treatment of the various gaseous exhaust species presents conflicting requirements. For example, lowering emissions of hydrocarbons and carbon monoxide are chemical oxidation problems while lowering emissions of NO x is a chemical reduction problem.
  • 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 present invention provides a process for maintaining or renewing the activity of a three-way catalytic converter.
  • the method for renewing or improving the performance of a three-way catalytic converter operated on a gasoline engine comprises: feeding a gasoline composition, comprising a blend of rhodium acetylacetonate and a fuel-soluble organo-platinum compound comprising diphenyl cyclooctadiene platinum(II) and/or platinum acetylacetonate, the platinum and rhodium compounds being present in amounts sufficient to provide a ratio of platinum to rhodium within the range of from 3:1 to 15:1, to a combustion chamber of the engine where the fuel is combusted 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; and passing the exhaust gases through the catalytic converter whereby rhodium and platinum are deposited in the catalytic converter to thereby renew it in terms of the ability to oxidize hydrocarbons and carbon monoxide and to reduce nitrogen oxides
  • 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 32,22 to 104,44°C (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 comprising diphenyl cyclooctadiene platinum(II) and/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.
  • 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.
  • the rhodium and platinum acetylacetonate compounds are commercially available and easily synthesized.
  • the composition will be temperature stable, and substantially free of phosphorus, arsenic, antimony, or halides.
  • 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)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (1)

  1. Verfahren zur Erneuerung oder Verbesserung der Leistung eines in einem Benzinmotor betriebenen Dreiwegekatalysators, umfassend
    Zufuhr einer Benzinzusammensetzung, umfassend ein Gemisch aus Rhodiumacetylacetonat und einer in Kraftstoff löslichen Organoplatinverbindung, welche Diphenylcyclooctadienplatin (II) und/oder Platinacetylacetonat umfaßt, wobei die Platin- und Rhodiumverbindungen in Mengen vorhanden sind, die ausreichen, um ein Verhältnis von Platin zu Rhodium im Bereich von 3:1 bis 15:1 bereitzustellen, zu einer Verbrennungskammer des Motors, in der der Kraftstoff verbrannt wird und die organischen Anteile der Rhodium- und Platinverbindungen oxidiert werden, wodurch das Rhodium und das Platin als aktive Katalysatorspezies in den durch die Verbrennung erzeugten Abgasen freigesetzt werden; und
    Leiten der Abgase durch den Katalysator, wodurch Rhodium und Platin in dem Katalysator abgeschieden werden, um dadurch dessen Fähigkeit, Kohlenwasserstoffe und Kohlenmonoxid zu oxidieren und Stickoxide zu reduzieren, zu erneuern.
EP98908457A 1997-01-31 1998-01-30 Verfahren zur verminderung von emissionen eines mit einem dreiwegekatalysator ausgerüsteten benzinmotors Expired - Lifetime EP0970165B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US79229797A 1997-01-31 1997-01-31
US792297 1997-01-31
PCT/US1998/001728 WO1998033871A1 (en) 1997-01-31 1998-01-30 Method and composition for reducing emissions from a gasoline engine equipped with a three-way catalytic converter

Publications (3)

Publication Number Publication Date
EP0970165A1 EP0970165A1 (de) 2000-01-12
EP0970165A4 EP0970165A4 (de) 2001-01-24
EP0970165B1 true EP0970165B1 (de) 2004-11-24

Family

ID=25156415

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98908457A Expired - Lifetime EP0970165B1 (de) 1997-01-31 1998-01-30 Verfahren zur verminderung von emissionen eines mit einem dreiwegekatalysator ausgerüsteten benzinmotors

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)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0126990D0 (en) 2001-11-09 2002-01-02 Carroll Robert Method and composition for improving fuel consumption
US20080318765A1 (en) * 2007-06-19 2008-12-25 Aradi Allen A Nanoalloys in emissions control after-treatment systems
US9341464B2 (en) 2011-10-17 2016-05-17 Atlas5D, Inc. Method and apparatus for sizing and fitting an individual for apparel, accessories, or prosthetics
US9511355B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) System and methods for using synergized PGM as a three-way catalyst
US20140274662A1 (en) 2013-03-15 2014-09-18 Cdti Systems and Methods for Variations of ZPGM Oxidation Catalysts Compositions
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
US9604175B2 (en) 2014-06-06 2017-03-28 Clean Diesel Technologies, Inc. Three-way catalyst systems including Nb—Zr—Al-mixed oxide supports, Ba—Pd, and Rh—Fe 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
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

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

Also Published As

Publication number Publication date
EP0970165A1 (de) 2000-01-12
WO1998033871A1 (en) 1998-08-06
US20010001354A1 (en) 2001-05-24
DE69827778T2 (de) 2005-11-10
DE69827778D1 (de) 2004-12-30
ES2232936T3 (es) 2005-06-01
EP0970165A4 (de) 2001-01-24
ATE283333T1 (de) 2004-12-15
TW499475B (en) 2002-08-21

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