EP0466512B1 - Procédé d'opérer un moteur à combustion interne - Google Patents

Procédé d'opérer un moteur à combustion interne Download PDF

Info

Publication number
EP0466512B1
EP0466512B1 EP91306360A EP91306360A EP0466512B1 EP 0466512 B1 EP0466512 B1 EP 0466512B1 EP 91306360 A EP91306360 A EP 91306360A EP 91306360 A EP91306360 A EP 91306360A EP 0466512 B1 EP0466512 B1 EP 0466512B1
Authority
EP
European Patent Office
Prior art keywords
gasoline
hydrocarbons
volume
fuel
boiling range
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
EP91306360A
Other languages
German (de)
English (en)
Other versions
EP0466512A1 (fr
EP0466512B2 (fr
Inventor
Thomas Albert Leeper
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.)
Ethyl Corp
Original Assignee
Ethyl Corp
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=24203896&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0466512(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ethyl Corp filed Critical Ethyl Corp
Publication of EP0466512A1 publication Critical patent/EP0466512A1/fr
Publication of EP0466512B1 publication Critical patent/EP0466512B1/fr
Application granted granted Critical
Publication of EP0466512B2 publication Critical patent/EP0466512B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G 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)
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number

Definitions

  • This invention relates to a process of operating a spark ignition internal combustion engine, i.e. a gasoline engine, with gasoline fuels having superior environmental and performance properties in use.
  • United States Patent No. 4139349 describes lead-free gasoline compositions comprising a synergistic combination of dicyclopentadienyl iron and cyclopentadienyl manganese tricarbonyl anti-knocks.
  • the invention is believed to provide a most effective and efficient way of using gasolines of suitable octane values while concomitantly reducing the potential for ground ozone formation, smog formation, and other grievous consequences of atmospheric pollution by reducing the maximum reactivity of exhaust products emitted by spark-ignition internal combustion engines.
  • this invention provides a process of operating a spark-ignition internal combustion engine with reduced reactivity of the tailpipe exhaust products which comprises using as the gasoline fuel for said engine a formulated lead-free gasoline comprising (i) a plurality of hydrocarbons of the gasoline boiling range containing not more than 30 volume % of aromatics and (ii) at least one cyclopentadienyl manganese tricarbonyl compound in an amount equivalent to up to 1/32 gram of manganese per gallon (3.78 litres).
  • the invention also provides the use of a said manganese compound (ii) in a said lead-free gasoline to reduce the reactivity of tailpipe exhaust products produced on combustion of said gasoline in a spark-ignition internal combustion engine.
  • the gasoline-type hydrocarbon fuels used in forming the gasoline will generally comprise saturates, olefins and aromatics; and they may also contain oxygenated fuel blending components, such as hydrocarbyl ethers.
  • the fuels contain a limitation on the content of aromatic gasoline hydrocarbons, inasmuch as aromatics are capable of providing exhaust product species of relatively high reactivity.
  • aromatic gasoline hydrocarbons in the base blends.
  • aromatic hydrocarbons such as benzene
  • carcinogens are regarded as carcinogens.
  • aromatic hydrocarbons and also olefinic hydrocarbons
  • exhaust products containing relatively reactive species which are deemed to participate in the formation of ground level ozone, smog, and other forms of atmospheric pollution.
  • This invention overcomes this dilemma by utilizing an antiknock compound of such potency that as little as 1/32 of a gram or less per gallon (3.78 litres) manganese in the fuel gives rise to significant increases in octane quality.
  • the refiner is able to provide a gasoline having the desired octane quality while at the same time maintaining or even reducing the quantity of aromatics in the base fuel.
  • the hydrocarbon tailpipe emissions resulting from use of the fuels of this invention have lower maximum reactivity than the hydrocarbon emissions of the same fuel would have if the antiknock agent were replaced by an amount of aromatic hydrocarbons necessary to achieve the same octane quality.
  • the fuels of this invention produce hydrocarbon emissions having substantially lower total maximum reactivities than the hydrocarbon emissions from the same base fuel devoid of the cyclopentadienyl manganese tricarbonyl additive(s).
  • This especially preferred embodiment of the invention is illustrated in Example 4 hereinafter.
  • the amount of olefinic hydrocarbons in the fuel composition can be controlled so as to be less than about 10% by volume (preferably less than 5% by volume) and, in addition, oxygenated fuel-blending components (e.g., hydrocarbyl ethers) of suitable distillation characteristics can be included in the fuel.
  • oxygenated fuel-blending components e.g., hydrocarbyl ethers
  • the fuel composition should be blended from components such that the Reid vapor pressure (ASTM test method D-323) is 62.1 kPa (9.0 psi) or less and most preferably 55.2 kPa (8.0 psi) or less. In this way the evaporative losses of the fuel into the atmosphere during storage and fueling operations can be effectively reduced.
  • Reid vapor pressures are determined at 100°F (37.8°C).
  • the gasolines of this invention are lead-free in the sense that no organolead antiknock agent is blended into the fuel. If any trace amounts of lead are present, such amounts are due exclusively to contamination in the system in which the fuels are formed, blended, stored, transported or dispensed.
  • the hydrocarbonaceous gasoline base stocks that can be used in forming the gasoline blends include straight run stocks, light naphtha fractions, cracked gasoline stocks obtained from thermal or catalytic cracking, hydrocracking, or similar methods, reformate obtained by catalgic reformation or like processes, polymer gasolines formed via polymerization or olefins, alkylates obtained by addition of olefins to isobutane or other hydrocarbons by alkylation processes, isomerates formed by isomerization of lower straight chain paraffins such as a n-hexane, n-heptane, and the like, and other hydrocarbons of the gasoline boiling range formed by suitable refinery processing operations.
  • Suitable amounts of appropriate hydrocarbons formed by other methods such as production from coal, shale ortarsands can be included, if desired.
  • reformates based on liquid fuels formed by the Fischer-Tropsch process can be included in the blends.
  • the resultant gasoline must satisfy the reduced maximum reactivity tailpipe hydrocarbon emission requirements of this invention and additionally will possess the distillation characteristics typical of conventional regular, midgrade, premium, or super-premium unleaded gasolines.
  • the motor gasolines are generally within the parameters of ASTM D 4814 and typically have initial boiling points in the range of 21-46°C (70-115°F) and final boiling points in the range of 188-227°C (370-440°F) as measured by the standard ASTM distillation procedure (ASTM D 86).
  • the hydrocarbon composition of gasolines according to volume percentages of saturates, olefins, and aromatics is typically determined by ASTM test procedure D 1319.
  • the base gasoline will be a blend of stocks obtained from several refinery processes.
  • the final blend may also contain hydrocarbons made by other procedures such as alkylates made by the reaction of C, olefins and butanes using an acid catalyst such as sulfuric acid or hydrofluoric acid, and aromatics made from a reformer.
  • the saturated gasoline components comprise paraffins and naphthenates. These saturates are generally obtained from: (1) virgin gasoline by distillation (straight run gasoline), (2) alkylation processes (alkylates), and (3) isomerization procedures (conversion of normal paraffins to branched chain paraffins of greater octane quality). Saturated gasoline components also occur in so-called natural gasolines. In addition to the foregoing, thermally cracked stocks, catalgically cracked stocks and catalgic reformates contain some quantities of saturated components. In accordance with preferred embodiments of this invention, the base gasoline blend contains a major proportion of saturated gasoline components. Generally speaking, the higher the content of saturates consistent with producing a fuel of requisite octane quality and distillation characteristics, the better.
  • Olefinic gasoline components are usually formed by use of such procedures as thermal cracking, and catalgic cracking. Dehydrogenation of paraffins to olefins can supplement the gaseous olefins occurring in the refinery to produce feed material foreither polymerization or alkylation processes.
  • the olefins if used in the fuel blends, should be substantially straight chain 1-oiefins such as 1-heptene, 1-octene, 1-nonene, and 1-decene. Olefins of this type are known to exhibit excellent antiknock response to cyclopentadienyl manganese tricarbonyls -- see Brown and Lovell, Industrial and Engineering Chemistry, Volume 50, No. 10, October 1958, pages 1547-50.
  • the gasoline base stock blends with which the cyclopentadienyl manganese tricarbonyl additive is blended pursuant to this invention will generally contain 40-90 volume % of saturates, up to 30 (and preferably less than 10 and more preferably less than 5) volume % olefins, and up to 30% by volume of aromatics, still more preferably no more than 28% by volume of aromatics, and most preferably no more than 25% by volume of aromatics.
  • the overall fuel blend will contain no more than 1% by volume and most preferably no more than 0.8% by volume of benzene.
  • Particularly preferred unleaded gasolines produced and/or utilized in the practice of this invention not only meet the emission reactivity criteria of this invention, but in addition, are characterized by having (1) a maximum sulfur content of 300 ppm, (2) a maximum bromine number of 20, (3) a maximum aromatic content of 20% by volume, (4) a maximum content of benzene of 1% by volume, and (5) a minimum content of contained oxygen of 1% by weight in the form of at least one monoether or polyether, such gasoline having dissolved therein up to 1/32 gram of manganese per gallon (3.78 litres) as methylcyclopentadienyl manganese tricarbonyl.
  • Gasolines of this type not containing the manganese additive are sometimes referred to as reformulated gasolines. See for example Oil & Gas Journal, April 9, 1990, pages 43-48.
  • the preferred gasoline base stock blends are those having an octane rating of (R + M)/2 ranging from 78-95.
  • any of a variety of cyclopentadienyl manganese tricarbonyl compounds can be used in the practice of this invention.
  • Illustrative examples of the manganese compounds which can be utilized in accordance with this invention include cyclopentadienyl manganese tricarbonyl, methyl-cyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadie- nyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl,
  • the preferred compounds or mixtures of compounds are those which are in the liquid state of aggregation at ordinary ambient temperatures, such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, and mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl.
  • the most preferred compound because of its commercial availability and its excellent combination of properties and effectiveness is methylcyclopentadienyl manganese tricarbonyl.
  • the maximum reactivity of the C l -C lo hydrocarbon species emitted from an operating engine is determined utilizing the ozone reactivity values developed by William P. L. Carter of the Air Pollution Research Center, University of California, at Riverside, California.
  • the methodology involves operating the vehicle on a chassis dynamometer (e.g., a Clayton Model ECE-50 with a direct-drive variable-inertia flywheel system which simulates equivalent weight of vehicles from 454 to 4026 kg (1000 to 8875 pounds) in 57 kg (125-pound) increments) in accordance with the Federal Test Procedure (United States Code of Federal Regulations, Title 40, Part 86, Subparts A and B, sections applicable to light-duty gasoline vehicles).
  • a chassis dynamometer e.g., a Clayton Model ECE-50 with a direct-drive variable-inertia flywheel system which simulates equivalent weight of vehicles from 454 to 4026 kg (1000 to 8875 pounds) in 57 kg (125-pound) increments
  • the Federal Test Procedure United States Code of Federal Regulations, Title 40, Part 86, Subparts A and B, sections applicable to light-duty gasoline vehicles.
  • the exhaust from the vehicle is passed into a stainless steel dilution tunnel wherein it is mixed with filtered
  • Samples of regulated emissions and samples for speciation of C l -C lo hydrocarbons are sampled from the diluted exhaust by means of a constant volume sampler (CVS) and are collected in bags (e.g., bags made from Tedlar resin) in the customary fashion.
  • CVS constant volume sampler
  • the Federal Test Procedure utilizes an urban dynamometer driving schedule which is 1372 seconds in duration. This schedule, in turn, is divided into two segments; a first sequent of 505 seconds (a transient phase) and a second segment of 867 seconds (a stabilized phase). The procedure calls for a cold-start 505 segment and stabilized 867 segment, followed by a ten-minute soak then a hot-start 505 segment. In the methodology used herein, separate samples for regulated emissions and for C l -C lo hydrocarbon speciation are collected during the cold-start 505 segment, the stabilized 867 segment, and the hot-start 505 segment.
  • the sampling system will include an impinger collection system (note Figure 2) enabling collection of exhaust samples continuously during the desired test cycles.
  • the air-diluted exhaust is bubbled at a rate of four liters per minute through chilled glass impingers containing an acetonitrile solution of 2,4-dinitrophenylhydrazine and perchloric acid.
  • the Federal Test Procedure cycle is extended to include a four-cycle procedure for sampling the aldehydes and ketones.
  • the sampling schedule when sampling for (a) regulated emissions, (b) hydrocarbon speciation, and (c) aldehydes and ketones involves collecting samples for (a) during the cold-start 505 segment, the stabilized 867 segment, and the hot-start 505 segment. Samples for (b) are also separately collected during these three segments. However, a sample for (c) is collected continuously during the cold-start 505 segment plus the stabilized 867 segment, and another sampling is started at the beginning of the hot-start 505 segment and is extended through the ensuing stabilized 867 segment. If it is only desired to sample for (a) and for (b), the impinger system and sampling procedure associated therewith are not used.
  • Example 1 The analytical procedures used to conduct the hydrocarbon speciation are described in Example 1 hereinafter.
  • MMT Fuel methylcyclopentadienyl manganese tricarbonyl
  • the constant volume sampler (CVS) used for the valuations was employed in conjunction with an 18-inch (45.7 cm) diameter by 16-foot (4.9 m) long stainless steel dilution tunnel (note Figure 1) and was run at a nominal 320 scfm (9062 I/min). This flow rate generally provided tunnel sampling zone temperatures not exceeding 110°F (43°C) during the Federal Test Procedures.
  • a cooling fan of 5000 cfm (142 m 3 /min) capacity was used in front of the vehicle during all test cycles. The hood was maintained fully open during all cycles and was closed during the soak periods. Exhaust sampling was conducted employing a system used in accordance with the guidelines established in the studies reported in the following papers and reports:
  • Table 3 summarizes the hydrocarbon speciation procedures in these tests.
  • Dilute exhaust emissions were sampled in Tedlar bags and analyzed by gas chromatography (GC) with a flame ionization detector (FID).
  • the compounds that were analyzed included methane, ethane, ethylene, acetylene, propane, propylene, benzene, and toluene.
  • the GC system was,equipped with four separate packed columns which are used to resolve the individual compounds.
  • a system of timers, solenoid valves, and gas sampling valves direct the flow of the sample through the system.
  • the carrier gas is helium. Peak areas are compared to an external calibration blend and the hydrocarbon concentrations are obtained using a Hewlett-Packard 3353 computer system.
  • Minimum detection limits for C 1 to C 3 compounds, benzene, and toluene are 0.05. ppmC.
  • the procedure used provides separations and concentration data for seven C 4 compounds, namely: isobutane, butane, 1-butene, isobutene, cis-2-butene, trans-2-butene and 1,3-butadiene.
  • Standard constant volume sampler (CVS) bag samples and evaporative emission bag samples were analyzed for the C 4 compounds using a GC equipped with an FID.
  • the GC system utilized a Perkin-Elmer Model 3920B GC with an FID, two pneumatically-operated and electrically-controlled Seiscorvalves, and an analytical column. This column is a 9 ft x 1/8-in.
  • the GC system utilizes a Perkin-Elmer Model 3920B GC equipped with subambient capabilities, a capillary column, and an FID.
  • the capillary column used in the system is a Perkin-Elmer F-50 Versilube, 150-ft x 0.02-in (46m x 0.5 mm) WCOT stainless steel column.
  • the column is initially cooled to - 139°F (-95°C) for sample injection. Upon injection, the temperature is programmed at a 7°F (4°C) increase per minute to 185°F (85°C).
  • the column temperature is held at 185°F (85°C) for approximately 15 minutes to complete column flushing.
  • a flow controller is used to maintain a 1.5 mL/min helium carrier flow rate. The 10 mL sample volume permits determination of 0.1 ppmC with the flame ionization detector.
  • Table 4 summarizes the total maximum reactivity data so determined.
  • Example 1 The procedure of Example 1 was repeated using as the base fuel a commercially-available unleaded regular gasoline from a different domestic oil company.
  • Table 5 summarizes the principal inspection data for the two test fuels blended therefrom - i.e., the MMT Fuel and the XY Fuel.
  • Example 1 The procedure of Example 1 was again repeated, this time using a commercially-available unleaded regular gasoline from a different domestic oil company containing 1 % by weight of contained oxygen in the form of an ether blending agent (believed to be methyl tert-butyl ether).
  • an ether blending agent (believed to be methyl tert-butyl ether).
  • the principal inspection data for the two test fuels blended from this base gasoline -- i.e., the MMT Fuel and the XY Fuel -- are summarized in Table 7.
  • the vehicle operated on the MMT Fuels emitted lower levels of hydrocarbons, carbon monoxide, and oxides of nitrogen than did the vehicle operated under the same test conditions on the XY Fuels.
  • the total maximum reactivities of the hydrocarbons emitted by the vehicle using the MMT Fuels was substantially lower than the total maximum reactivities of the hydrocarbons emitted by the vehicle which used the XY Fuels. It was also observed from the tests conducted as per Examples 1-3 above that the vehicle operated on the MMT Fuel generally produced lower emissions of aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde than the vehicle operated on the XY Fuels. Fuel economies were slightly lower (1-2%) for the MMT-fueled vehicle.
  • Example 9 presents the averaged results obtained in these runs.
  • the MMT Fuel of this invention not only produced less total hydrocarbon tailpipe emissions but even more importantly, the total maximum reactivity of the speciated hydrocarbon emissions from the MMT-fuel vehicle was substantially lower (28% lower) than the speciated hydrocarbon emissions from the clear (manganese-free) base fuel. Note also from Table 2 that the octane quality of the MMT Fuel was significantly higher than that of the clear base fuel, i.e., (R + M)/2 of 92.9 v. 92.2.
  • the fuels of this invention can contain one or more other additives provided such other additive or combination of additives does not excessively detract from the performance -- especially the improved exhaust emission performance such as is illustrated by Examples 1-4 -- exhibited by the same base fuel containing up to 1/32 of a gram of manganese per gallon when devoid of such other additive or additives.
  • Antioxidants, deposit-control additives e.g., induction system cleanliness additives, carburetor detergents, and ORI-control additives
  • corrosion inhibitors e.g., metal deactivators
  • oxygenated blending materials such as dihydrocarbyl ethers and polyethers, typify additives commonly utilized in gasolines, and which may be used in the fuels of this invention subject to the foregoing proviso.
  • this invention contemplates the inclusion in the fuel of any ancillary additive or combination of additives which contributes an improvement to the fuel or its performance and which does not destroy or seriously impair the performance benefits made possible by this invention.
  • Preferred oxygenated materials that can be blended into the fuels of this invention are ethers of suitable low volatility such as methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, and 2,2-diethyl-1,3-propanediol.
  • ethers of suitable low volatility such as methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, and 2,2-diethyl-1,3-propanediol.
  • mixtures of methyl hydrocarbyl ethers formed by catalytic methoxylation of olefin components in gasoline can be effectively utilized. Processes for producing such mixtures are known and reported in the literature. See for example U. S. Pat. No. 4,746,761, and WO 8911463, and references cited therein.
  • fuel-soluble esters and alcohols of suitably low volatility such as tert-butyl acetate, 1-hexanol, 2-hexanol, 3-hexanol, and polyethoxyethanols.
  • oxygenated compounds are employed in amounts sufficient to provide up to 3 to 4 weight % oxygen in the fuel, provided such usage is consistent with existing or proposed legislation.
  • suitable oxygen-containing blending agents include p-cresol, 2,4-xylene, 3-methoxyphenol, 2-methylfuran, cyclopentanone, isovaleraldehyde, 2,4-pentanedione and si mi lar oxygen-containing substances.
  • Preferred antioxidants for the fuels of this invention are hindered phenolic antioxidants, such as 2,6-di-tert-butyl-phenol, 2,4-dimethyl-6-tert-butylphenol, 4-methyi-2,6-di-tert-butyiphenoi, 4-ethyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, tert-butylphenol, and mixtures of tertiary butylated phenols predominating in 2,6-di-tert-butylphenol.
  • aromatic amine antioxidants can prove useful either alone or in combination with a phenolic antioxidant.
  • Antioxidants are usually employed in amounts of up to 25 pounds per thousand barrels (0.07 kg per m 3 ), the amount used in any given case being dependent upon the stability (e.g. olefin content) of the gasoline.
  • additives preferably utilized in the fuels of this invention are ashless detergents such as polyether amines, polyalkenyl amines, alkenyl succini mides, and polyether amide amines.
  • ashless detergents such as polyether amines, polyalkenyl amines, alkenyl succini mides, and polyether amide amines.
  • Such materials can be used at treat levels of 50 to 500 pounds per thousand barrels (0.14 to 1.4 kg per m 3 ), and more usually in the range of 100 to 200 pounds per thousand barrels (0.28 to 0.55 kg per m 3 ).
  • cyclopentadienyl manganese tricarbonyl compounds as well as the other supplemental additives or blending agents can be blended with the base fuels according to well known procedures utilizing conventional mixing equipment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (12)

1. Procédé pour faire fonctionner un moteur à combustion interne à allumage par étincelle avec une réactivité réduite des produits émis par le tuyau d'échappement, qui comprend l'utilisation comme carburant pour ledit moteur d'une essence formulée sans plomb comprenant (i) plusieurs hydrocarbures dans la plage d'ébullition de l'essence, ne contenant pas plus de 30 % en volume de produits aromatiques, et (ii) au moins un composé du type cyclopentadiényl-manganèse-tricarbonyle en une quantité équivalent à une valeur allant jusqu'à 1/32 grammes de manganèse par gallon (3,78 litres).
2. Procédé suivant la revendication 1, dans lequel les hydrocarbures dans la plage d'ébullition de l'essence comprennent des produits saturés, des oléfines et des produits aromatiques.
3. Procédé suivant la revendication 2, dans lequel les hydrocarbures, dans la plage d'ébullition de l'essence, de l'essence utilisée comprennent 40 à 80 % en volume de produits saturés et jusqu'à 25 % en volume de produits aromatiques, ainsi que moins de 1 % en volume de benzène.
4. Procédé suivant la revendication 1, 2 ou 3, dans lequel les hydrocarbures dans la plage d'ébullition de l'essence contiennent moins de 10 % en volume d'oléfines.
5. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'essence comprend au moins un constituant oxygéné de mélange au carburant.
6. Procédé suivant l'une quelconque des revendications précédentes, dans lequel le composé du type cyclopentadiényl-manganèse-tricarbonyle consiste essentiellement en méthylcyclopentadiényl-manganèse-tricarbonyle et dans lequel l'essence contenant du manganèse possède une tension de vapeur Reid (méthode d'essai ASTM D-323) égale ou inférieure à 55,2 kPa (8,0 Ib/in2).
7. Utilisation d'au moins un composé du type cyclopentadiényl-manganèse-tricarbonyle en une quantité équivalent à une valeur allant jusqu'à 1/32 gramme de manganèse par gallon (3,78 litres) dans un carburant formulé sans plomb consistant en une essence comprenant plusieurs hydrocarbures dans la plage d'ébullition de l'essence, ne contenant pas plus de 30 % en volume de produits aromatiques, pour réduire la réactivité des produits émis par le tuyau d'échappement, formés par combustion de ladite essence dans un moteur à combustion interne à allumage par étincelle.
8. Utilisation suivant la revendication 7, dans laquelle les hydrocarbures dans la plage d'ébullition de l'essence comprennent des produits saturés, des oléfines et des produits aromatiques.
9. Utilisation suivant la revendication 8, dans laquelle les hydrocarbures, dans la plage d'ébullition de l'essence, de l'essence utilisée comprennent 40 à 80 % en volume de produits saturés et jusqu'à 25 % en volume de produits aromatiques, ainsi que moins de 1 % en volume de benzène.
10. Utilisation suivant la revendication 7, 8 ou 9, dans laquelle les hydrocarbures dans la plage d'ébullition de l'essence contiennent moins de 10 % en volume d'oléfines.
11. Utilisation suivant l'une quelconque des revendications 7 à 10, dans laquelle l'essence comprend au moins un constituant oxygéné de mélange au carburant.
12. Utilisation suivant l'une quelconque des revendications 7 à 11, dans laquelle le composé du type cyclopentadiényl-manganèse-tricarbonyle consiste essentiellement en méthylcyclopentadiényl-manganèse-tricarbonyle et dans laquelle l'essence contenant du manganèse possède une tension de vapeur Reid (méthode d'essai ASTM D-323) égale ou inférieure à 55,2 kPa (8,0 Ib/in2).
EP91306360A 1990-07-13 1991-07-12 Utilisation d'au moins un composé du type cyclopentadiényl-manganèse-tricarbonyle dans un carburant formulé sans plomb. Expired - Lifetime EP0466512B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55209090A 1990-07-13 1990-07-13
US552090 1990-07-13

Publications (3)

Publication Number Publication Date
EP0466512A1 EP0466512A1 (fr) 1992-01-15
EP0466512B1 true EP0466512B1 (fr) 1994-06-29
EP0466512B2 EP0466512B2 (fr) 2003-07-02

Family

ID=24203896

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91306360A Expired - Lifetime EP0466512B2 (fr) 1990-07-13 1991-07-12 Utilisation d'au moins un composé du type cyclopentadiényl-manganèse-tricarbonyle dans un carburant formulé sans plomb.

Country Status (6)

Country Link
EP (1) EP0466512B2 (fr)
JP (1) JP3112990B2 (fr)
AU (1) AU651116B2 (fr)
CA (1) CA2045706C (fr)
DE (1) DE69102683T3 (fr)
ES (1) ES2055964T5 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1528097A3 (fr) * 2003-10-29 2005-07-13 Afton Chemical Corporation Procédé pour diminuer l'écaillage des dépôts de la chambre de combustion.
US6941743B2 (en) 2000-12-12 2005-09-13 Ethyl Corporation Lean burn emissions system protectant composition and method
US6971337B2 (en) 2002-10-16 2005-12-06 Ethyl Corporation Emissions control system for diesel fuel combustion after treatment system
US7101493B2 (en) 2003-08-28 2006-09-05 Afton Chemical Corporation Method and composition for suppressing coal dust
US7111591B2 (en) 2003-12-10 2006-09-26 Afton Chemical Corporation Method of improving the operation of combustion particulate filters
US7276094B2 (en) 2003-11-25 2007-10-02 Ethyl Petroleum Additives, Inc. Mixed metal catalyst additive and method for use in hydrocarbonaceous fuel combustion system
US7332001B2 (en) 2003-10-02 2008-02-19 Afton Chemical Corporation Method of enhancing the operation of diesel fuel combustion systems
EP2014745A1 (fr) 2007-07-10 2009-01-14 Afton Chemical Corporation Composition de combustible comprenant un composé à base de nitrogène
US8852299B2 (en) 2006-06-30 2014-10-07 Afton Chemical Corporation Fuel composition
US8852298B2 (en) 2006-06-29 2014-10-07 Afton Chemical Corporation Fuel composition containing iron and manganese to reduce spark plug fouling

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2076302C (fr) * 1991-08-23 2003-05-27 Thomas Albert Leeper Carburants a proprietes ameliorees
US5551957A (en) * 1992-05-06 1996-09-03 Ethyl Corporation Compostions for control of induction system deposits
US6242147B1 (en) 1997-09-03 2001-06-05 Minolta Co., Ltd. Negatively chargeable toner and developing device using thereof
JP5773220B2 (ja) * 2012-08-07 2015-09-02 トヨタ自動車株式会社 排ガスセンサ
JP5787180B2 (ja) * 2012-08-07 2015-09-30 トヨタ自動車株式会社 排ガスセンサ
US20170198229A1 (en) * 2016-01-13 2017-07-13 Afton Chemical Corporation Method and composition for improving the combustion of aviation fuels

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127351A (en) * 1964-03-31 Xxvii
US2818417A (en) * 1955-07-11 1957-12-31 Ethyl Corp Cyclomatic compounds
GB1145930A (en) * 1967-12-22 1969-03-19 Exxon Research Engineering Co Liquid fuel composition
US4437436A (en) * 1982-10-04 1984-03-20 Shell Oil Company Antiknock additive compositions and unleaded gasoline containing same
ATE69462T1 (de) * 1985-08-28 1991-11-15 William C Orr Bleifreie brennstoffzusammensetzung.

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6941743B2 (en) 2000-12-12 2005-09-13 Ethyl Corporation Lean burn emissions system protectant composition and method
US8006652B2 (en) 2002-10-16 2011-08-30 Afton Chemical Intangibles Llc Emissions control system for diesel fuel combustion after treatment system
US6971337B2 (en) 2002-10-16 2005-12-06 Ethyl Corporation Emissions control system for diesel fuel combustion after treatment system
US7101493B2 (en) 2003-08-28 2006-09-05 Afton Chemical Corporation Method and composition for suppressing coal dust
US7332001B2 (en) 2003-10-02 2008-02-19 Afton Chemical Corporation Method of enhancing the operation of diesel fuel combustion systems
EP1528097A3 (fr) * 2003-10-29 2005-07-13 Afton Chemical Corporation Procédé pour diminuer l'écaillage des dépôts de la chambre de combustion.
US7276094B2 (en) 2003-11-25 2007-10-02 Ethyl Petroleum Additives, Inc. Mixed metal catalyst additive and method for use in hydrocarbonaceous fuel combustion system
US7111591B2 (en) 2003-12-10 2006-09-26 Afton Chemical Corporation Method of improving the operation of combustion particulate filters
US8852298B2 (en) 2006-06-29 2014-10-07 Afton Chemical Corporation Fuel composition containing iron and manganese to reduce spark plug fouling
US8852299B2 (en) 2006-06-30 2014-10-07 Afton Chemical Corporation Fuel composition
EP2014745A1 (fr) 2007-07-10 2009-01-14 Afton Chemical Corporation Composition de combustible comprenant un composé à base de nitrogène
EP2363450A1 (fr) 2007-07-10 2011-09-07 Afton Chemical Corporation Composition de combustible comprenant un composé contenant de l'azote.
US8715373B2 (en) 2007-07-10 2014-05-06 Afton Chemical Corporation Fuel composition comprising a nitrogen-containing compound
US8734540B2 (en) 2007-07-10 2014-05-27 Afton Chemical Corporation Fuel composition comprising a nitrogen-containing compound

Also Published As

Publication number Publication date
ES2055964T3 (es) 1994-09-01
CA2045706C (fr) 2002-09-17
CA2045706A1 (fr) 1992-01-14
AU8016691A (en) 1992-01-16
JP3112990B2 (ja) 2000-11-27
ES2055964T5 (es) 2003-12-16
JPH04226597A (ja) 1992-08-17
EP0466512A1 (fr) 1992-01-15
DE69102683D1 (de) 1994-08-04
DE69102683T2 (de) 1994-10-20
AU651116B2 (en) 1994-07-14
EP0466512B2 (fr) 2003-07-02
DE69102683T3 (de) 2004-04-08

Similar Documents

Publication Publication Date Title
US5599357A (en) Method of operating a refinery to reduce atmospheric pollution
EP0466512B1 (fr) Procédé d'opérer un moteur à combustion interne
US5113803A (en) Reduction of Nox emissions from gasoline engines
USH1305H (en) Reformulated gasolines and methods of producing reformulated gasolines
EP0466511B1 (fr) Carburants à propriétés augmentées
US5511517A (en) Reducing exhaust emissions from otto-cycle engines
CA2076302C (fr) Carburants a proprietes ameliorees
JP5367149B2 (ja) 無鉛高オクタン価ガソリン
JP4429940B2 (ja) 無鉛ガソリン
McGinty et al. A review of the effect of petrol composition on unregulated motor vehicle emissions with particular emphasis on non-catalyst vehicles
JP5173697B2 (ja) 無鉛高オクタン価ガソリン及び無鉛高オクタン価ガソリンの製造方法
JP4856991B2 (ja) 無鉛高オクタン価ガソリン
JP3946276B2 (ja) ガソリン基材及び該基材を用いた無鉛ガソリン
JP5005989B2 (ja) 無鉛ガソリン
JP5117020B2 (ja) 無鉛ガソリン
JP4974618B2 (ja) 無鉛ガソリン
JP5173696B2 (ja) 無鉛高オクタン価ガソリン及び無鉛高オクタン価ガソリンの製造方法
Ufuk EFFECT OF OXYGENATE ADDITIVES INTO GASOLINE FOR IMPROVED FUEL PROPERTIES

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT

17P Request for examination filed

Effective date: 19920629

17Q First examination report despatched

Effective date: 19921211

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 69102683

Country of ref document: DE

Date of ref document: 19940804

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2055964

Country of ref document: ES

Kind code of ref document: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: MR. BILL ORR

Effective date: 19950323

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: MR. BILL ORR

Effective date: 19950323

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

RTI2 Title (correction)

Free format text: THE USE OF AT LEAST ONE CYLOPENTADIENYLMANGANESE TRICARBONYL COMPOUND IN A FORMULATED LEAD FRE GASOLINE FUEL.

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20030702

AK Designated contracting states

Designated state(s): BE DE ES FR GB IT

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20030708

Kind code of ref document: T5

ET3 Fr: translation filed ** decision concerning opposition
APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070726

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070831

Year of fee payment: 17

BECA Be: change of holder's address

Owner name: *AFTON CHEMICAL INTANGIBLES LLC330 SOUTH FOURTH ST

Effective date: 20060131

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070727

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070730

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070717

Year of fee payment: 17

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090203

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080712

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080731

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080714

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20100728

Year of fee payment: 20

BE20 Be: patent expired

Owner name: *AFTON CHEMICAL INTANGIBLES LLC

Effective date: 20110712