Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G 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 compositions and 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-Iigand 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 PtCI 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.
• 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- ⁇ 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 Ri and R 2 are, independently, benzyl, phenyl, nitrobenzyl or alkyl having 1 to 10 carbons, e.g., diphenyl cyclooctadiene platinum(ll).
• 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.
• the 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(ll) 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-
• X is a ligand containing at least one unsaturated carbon-to-carbon bond with an olefinic, acetylenic or aromatic pi bond configuration
• Ri 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.
• 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)

Applications Claiming Priority (3)

Publications (3)

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Family Applications (1)

Country Status (7)

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Family Cites Families (2)

• 1998
  • 1998-01-30 AT AT98908457T patent/ATE283333T1/de not_active IP Right Cessation
  • 1998-01-30 EP EP98908457A patent/EP0970165B1/fr not_active Expired - Lifetime
  • 1998-01-30 DE DE69827778T patent/DE69827778T2/de not_active Expired - Lifetime
  • 1998-01-30 WO PCT/US1998/001728 patent/WO1998033871A1/fr not_active Ceased
  • 1998-01-30 ES ES98908457T patent/ES2232936T3/es not_active Expired - Lifetime
  • 1998-02-02 TW TW087101108A patent/TW499475B/zh not_active IP Right Cessation
• 2001
  • 2001-01-08 US US09/756,383 patent/US20010001354A1/en not_active Abandoned

Non-Patent Citations (1)

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