EP0235280B1 - Composition de carburant sans plomb - Google Patents

Composition de carburant sans plomb Download PDF

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Publication number
EP0235280B1
EP0235280B1 EP86906042A EP86906042A EP0235280B1 EP 0235280 B1 EP0235280 B1 EP 0235280B1 EP 86906042 A EP86906042 A EP 86906042A EP 86906042 A EP86906042 A EP 86906042A EP 0235280 B1 EP0235280 B1 EP 0235280B1
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Prior art keywords
fuel composition
gasoline
volume percent
fuel
group
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EP0235280A1 (fr
EP0235280A4 (fr
EP0235280B2 (fr
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William C. Orr
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ORR William C
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ORR William C
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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
    • C10L1/02—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—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

  • This invention relates generally to novel fuel compositions for spark ignition internal combustion engines. More particularly, it relates to a novel additive combination for "nonleaded" gasoline compositions.
  • organo-metallic compounds as antiknock agents in fuels for high compression, spark ignited, internal combustion engines has been practiced for some time.
  • organo-metallic compound used for this purpose is tetraethyl lead (“TEL").
  • TEL tetraethyl lead
  • these organo-metallic compounds have served well as antiknock agents.
  • certain environmental hazards are now associated with the alkyl lead components of these compounds. This circumstance has precipitated a series of Environmental Protection Agency ("EPA") mandates aimed at completely phasing out leaded gasolines.
  • EPA Environmental Protection Agency
  • organo-metallic compounds such as cyclomatic manganese tricarbonyls, particularly methylcyclopentadienyl manganese tricarbonyl ("MMT"), were once accepted alternatives to TEL.
  • MMT methylcyclopentadienyl manganese tricarbonyl
  • TEL methylcyclopentadienyl manganese tricarbonyl
  • these compounds produced another set of environmental problems. Their use tends to steadily increase the amount of unoxidized and/or partially oxidized hydrocarbons. Fuels containing such organomanganese compounds gradually cause the emission of substantially higher levels of hydrocarbons than are permitted under law.
  • the 195 patent points out that when lower aliphatic alcohols and TEL type compounds are present together in petroleum hydrocarbon gasolines, the antiknock effect achieved by the combination is substantially lower than would be expected in view of their known individual antiknock efficacies. This phenomena is commonly referred to as "negative lead susceptibilities".
  • the 195 patent teaches that a positive synergism in the antiknock properties of leaded gasoline/alcohol fuel compositions can be obtained by adding a cyclomatic manganese tricarbonyl such as MMT to leaded gasoline compositions.
  • MMT cyclomatic manganese tricarbonyl
  • the technical advantages produced by such fuel compositions are being effectively negated by the phase out of lead containing antiknock additives.
  • Blending octane value is the arithmetic average of the research octane value and the motor octane value and is typically expressed as (R + M)/2.
  • methanol/gasoline blends have been reported to be 2 to 3 Motor Octane Number and as high as 16 Research Octane Number above the reported values for the base gasoline.
  • finished methanol/gasoline fuels normally are 1.5 to 3 octane points (R+M)/2 higher than the base fuel itself. See for example, Eccleston, B.H. and Cox, F.W., PHYSICAL PROPERTIES OF GASOLINE/METHANOL MIXTURES, Bartlesville Energy Research Center, Bartlesville, Oklahoma (1977).
  • methanol by itself is not widely used as a gasoline additive due to the number of serious technical and legal problems associated with its use.
  • the presence of even small amounts of water can cause serious operational problems.
  • Methanol when used by itself tends to phase-separate from gasoline in the presence of water and/or when exposed to cold weather conditions. This tendency to phase-separate has been an obstacle to the use of such alcohols as octane enhancers and gasoline extenders.
  • methanol, particularly when it has phase-separated from gasoline is known to have harmful corrosive tendencies to certain fuel delivery and engine components.
  • Section 211(f)(a) of the Clean Air Act governs the usage and introduction of additives in unleaded gasolines and specifically provides that no fuel or fuel additive may be first introduced into commerce that is not "substantially similar" to any fuel or fuel additive used in the certification of any 1974 or later model year vehicle.
  • EPA defined "substantially similar” to include fuels with up to 2.0 wt. percent oxygen. Ethers or alcohols (except methanol) are acceptable additives if they otherwise meet these oxygen limitations.
  • Methanol can be used as a de-icer when used up to 0.3 volume percent or be used for this purpose up to 2.75 volume percent when introduced with an equal volume of butanol or a higher molecular weight alcohol.
  • the fuel must conform to the characteristics of an unleaded gasoline as specified by ASTM D 439.
  • This definition of “substantially similar” provides a general rule for the inclusion of oxygenates in unleaded gasolines.
  • Methyl tertiary butyl ether (MTBE) qualifies under the general 2% oxygen rule. This is equivalent to about 11 % MTBE by volume, depending on the specific gravity of the gasoline.
  • the Clean Air Act under Section 211 (f)(4) provides that the EPA Administrator may waive the prohibition on new fuels or fuel additives. However, prior to granting a waiver the Administrator must determine if the application meets the burden of demonstrating that the new fuel or fuel additive will not cause the failure of an emission control system or an emission standard(s). Under this section of the Act, the Administrator has both denied and granted several waiver requests.
  • methanol is 50 percent by weight oxygen.
  • Fuel introduction and delivery systems e.g., fuel injection systems, carburetors
  • a predetermined stoichiometric amount (ratio) of air to fuel and hence the amount of oxygen to fuel.
  • this predetermined stoichiometric ratio is calculated without regard for gasolines containing oxygen. If a gasoline contains excessive concentrations of oxygenated components such as methanol, the air (oxygen) to fuel ratio is significantly changed from the predetermined ratio. Significant deviations from the predetermined ratio causes poor ignition and combustion properties of the fuel. A high air (oxygen) to fuel ratio produced in this manner will cause the engine to run lean. If an engine's air (oxygen) to fuel ratio becomes too high or lean, the engine will fail to start and/or continue to run.
  • Technical enleanment An attribute of enleanment which heretofore has not been distinguished by those skilled in the art is called “technical enleanment”.
  • Technical enleanment is that unexpected phenomena which exhibits symptoms of enleanment occurring when the total air (oxygen) content of the finished fuel is not stoichiometrically or chemically lean. Such behavior is very similar to enleanment and includes engine stalling, lack of power, poor combustion, difficult start-ups (especially warm start-ups) and other problems normally associated with alcohol/gasoline fuels and combustion/fuel systems which are known to be chemically or stoichiometrically lean.
  • alcohols typically increase Reid vapor pressure, depress the initial fraction of the distillation curve, together tending to increase evaporative emissions.
  • methanol at 5 to 10 volume percent concentrations increases the blended fuel's vapor pressure from 105.5 to 246.0 grams/cm2 (1.5 to 3.5 p.s.i.) over the base fuel itself.
  • This negative characteristic is known in the art as a nonideal positive vapor pressure increase, because heat methanol has a vapor pressure lower than that of the base gasoline to which it is blended.
  • other lower molecular weight alcohols tend to exhibit similar nonideal vapor pressure attributes.
  • aromatic hydrocarbons particularly in streams or fractions thereof in the range of C 8 -C 25 and subparts thereof have heretofore been generally precluded from accepted usage in normal boiling range gasolines due to their high boiling temperatures and potentially harmful emissions.
  • the use of these aromatic materials have traditionally been used as refinery intermediates and as components in gas oils, fuel oils, distillates and the like.
  • Some of these aromatic hydrocarbons are recycle oils (cycle oils) from the catalytic cracker which are utilized as components in diesel fuel oils.
  • recycle oils (cycle oils) from the catalytic cracker which are utilized as components in diesel fuel oils.
  • Light cycle oils, the lighter fraction of cycle oils typically have low cetane numbers but high octane numbers. The low cetane numbers make these fuels less attractive for diesel fuel, but their boiling temperatures and other attributes precludes their usage in gasolines.
  • cyclomatic manganese tricarbonyls such as MMT are directly traceable to the associative build-up of unoxidized or partially oxidized hydrocarbons and oxides of manganese (believed to be "Mn3O4.”).
  • the oxide of manganese is the oxidation product of the cyclomatic manganese tricarbonyls.
  • HGM hydrocarbon gum material
  • HGM tends to attract other unoxidized or partially oxidized hydrocarbons and Mn 3 0 4 which together tend to plug catalysts, foul spark plugs and form combustion chamber deposits. It is also believed, especially when the quantities of MMT are in excess of about 0.0165 grams per litre, (1/1.6 grams per gallon) that the presence of HGM causes a certain type of Mn304 deposit in the catalytic converter system which ultimately causes it to plug.
  • the defined operational range of proportions over which the gasoline bases, the C 1 to C 6 aliphatic alcohol component, the cyclopentadienyl manganese tricarbonyl component and the aromatic hydrocarbon component may be employed to reduce hydrocarbon and evaporative emissions, correct technical enleanment and improve RVP, control initial and mid-range distillation depression and control end boiling point temperatures is:
  • the beneficial hydrocarbon emission and other ameliorative effects of this invention do not generally begin to occur until approximately 1.0% oxygen by weight of the C, to C 6 alcohol component is introduced into the fuel composition.
  • methanol When methanol is used as the sole aliphatic alcohol without the benefit of any cosolvent(s) it should be limited to a concentration of about 5 volume percent or less of the fuel composition.
  • a cosolvent or group of cosolvents selected from the group consisting of C 2 to C 12 aliphatic alcohols, C 3 to C 12 ketones and/or C 2 to C 12 ethers in concentrations from about 1 to about 20 volume percent should also be employed.
  • the combined methanol and cosolvent concentration should, however, not exceed 30 volume percent of the entire fuel composition.
  • the cosolvent alcohol(s) is selected from the group consisting of C 2 to C 8 aliphatic alcohols
  • the preferred aliphatic alcohol is a saturated aliphatic alcohol(s).
  • one or more C, to C 6 aliphatic alcohols preferably, C, to C 6 saturated aliphatic alcohols, must be employed in the fuel composition.
  • the alcohol component maybe any individual alcohol or any combination or mixture thereof. Mixed alcohol combinations may be desirable for enhancing blending octane values and controlling RVP increases.
  • mixed alcohols produced from the modification of known methanol catalysts use of alkali metal oxide catalysts, use of rhodium catalysts, isosynthesis using alkalized Th0 2 catalysts, use of modified Fischer-Tropsch catalysts, modified turgi catalysts, and/or produced from certain isomerization/dehydrogenation processes, olefinic/hydration processes, "OXO" processes and the like, are acceptable.
  • Alcohol mixtures generally having methanol, ethanol, propanols, butanols, pentanols and hexanols in the composition; which by weight percent of the composition decline as the individual molecular weight of the alcohol increases, are desirable.
  • An example of a mixed alcohol composition wherein the lower molecular weight alcohols have a higher relative proportion of the composition by volume percent than do the higher molecular alcohols include: methanol at approximately 50 weight percent of the alcohol component, ethanol at approximately 25 weight percent, propanols at approximately 13 weight percent, butanols at approximately 6 weight percent, pentanols at approximately 3 weight percent, with hexanols and other higher alcohols generally representing the balance of the alcohol component.
  • a desirable alcohol mixture would include a composition wherein the higher molecular weight alcohols have higher relative proportions by volume percent of the composition than do the lower molecular weight alcohols. Still another example would include a mixed alcohol composition wherein similar proportions of each alcohol exist by volume percent in the composition. Mixed alcohol compositions generally include methanol to higher alcohol ratios generally varying from 4:1 to 1:4 weight percent of the alcohol compositions. Those other combinations of alcohol mixtures which positively effect RVP, octane, distillation characteristics, end boiling point temperatures, and/or emissions are particularly desirable.
  • Suitable alcohols for use include methanol, ethanol, N-propanol, isopropanol, N-butanol, secondary- butanol, isobutanol, tertiary butanol, pentanols, hexanols and the like.
  • aliphatic alcohols in ranges from up to about 30.0% by volume with about up to 14.2% oxygen by weight give excellent hydrocarbon emission results when used in unleaded gasolines.
  • the composition should have at least 0.000264 grams per litre (0.001 grams per gallon) manganese and generally no more than 0.2642 grams per litre (one gram per gallon) manganese of a cyclomatic manganese tricarbonyl compound.
  • the alcohol employed should be anhydrous, but alcohols containing small amounts of water can also be used. Within the preferred concentration range most of the C, to C 6 aliphatic alcohols are completely miscible with petroleum hydrocarbons and it is preferred that such alcohols be used in amounts within their solubility limits. However, if desirable, an amount of alcohol in excess of its solubility can be incorporated in the fuel by such means, as for example, by use of mutual solvents.
  • An acceptable cyclomatic manganese tricarbonyl concentration range is from about 0.000264 to about 0.2642 grams manganese per litre. of fuel composition.
  • a more acceptable range is from about 0.004 to about 0.132 grams manganese per litre (about 1/64 to about 1/2 grams per gallon) of composition.
  • a more desirable and preferred range is from about 0.004 to about 0.066 grams manganese per litre (about 1/64 to about 1/4 grams manganese per gallon) of composition.
  • An even more preferred range is from about 0.004 to about 0.033 grams manganese per litre (about 1/64 to about 1/8 grams manganese per gallon) of composition.
  • the preferred cyclomatic manganese tricarbonyl used in the composition is methyl cyclopentadienyl manganese tricarbonyl (MMT).
  • the acceptable oxygen by weight in the fuel composition is up to about 14.2 weight percent. A more desirable range would be from about 1.0 to about 8.0 weight percent. A preferred range would be from about 1.0 to about 5.0 weight percent. The most preferred range is from about 2.0 to about 3.5 weight percent of the fuel composition.
  • An acceptable range of aromatic hydrocarbons is up to about 45 percent.
  • a desirable range is from about 1.0 to about 20 volume percent of the composition.
  • a preferred range would be from about 1.0 to about 10.0 volume percent of the composition.
  • a more preferred range would be from about 1.0 to about 5.0 volume percent of the composition.
  • An acceptable boiling range of the aromatic hydrocarbons including streams or fractions containing aromatic hydrocarbons is up to about 370 C (700 F).
  • a more acceptable range is from about 90 °C (200 °F) to about 290 °C (550 °F).
  • a preferred range is from about 90 °C (200 F) about 260 °C (500 F), and a more preferred range is from 120° C (250° F) to about 230° C (450° F).
  • Preferred end point boiling ranges are from approximately 200° C (400° F) to 290° C (550° F).
  • Desirable individual alcohol compositions would contain from about up to about 5 volume percent methanol, or up to about 15 volume percent ethanol, or up to about 18 volume percent isopropanol, or up to about 18 volume percent normal propanol, or up to about 20 volume percent tertiary butanol, or up to about 20 volume percent secondary butanol, or up to about 20 volume percent isobutanol, or up to about 20 volume percent normal butanol, or kup to about 25 volume percent pentanols, or up to about 30 volume percent hexanols and aromatic hydrocarbons from up to about 20 volume percent together with MMT as the cyclopentadienyl manganese in a concentration of up to about 0.066 gram of manganese per litre (about 1/4 gram of manganese per gallon) of fuel composition.
  • MMT as the cyclopentadienyl manganese in a concentration of up to about 0.066 gram of manganese per litre (about 1/4
  • a more preferred composition would contain aromatic hydrocarbons from about 1.0 to about 10 volume percent and a MMT concentration from about 0.004 to about 0.033 grams of manganese per litre (about 1/64 to about 1/8 grams of manganese per gallon) of fuel composition.
  • a desirable alcohol/gasoline fuel composition includes a C 1 - C 6 alcohol component from about 2 to 30 volume percent, plus about 0.004 to 0.264 grams manganese of MMT per litre (about 1/64 to 1 gram manganese of MMT per gallon) of the composition with about 1 to about 45 volume percent aromatic hydrocarbons together with unleaded gasoline.
  • a more desirable composition would contain aromatic hydrocarbons from about 1 to about 20 volume percent together with MMT from about 0.004 to 0.066 grams manganese of MMT per litre (about 1 64 to 14 gram manganese of MMT per gallon) of the composition.
  • a desirable alcohol (cosolvent)igasoline fuel composition includes a Ci - C 6 alcohol component from about 2 to 25 volume percent of the composition plus a cosolvent or group of cosolvents selected from the group consisting of C 2 - C 12 aliphatic alcohols, C 3 - C 12 ketones and/or C 2 to C 12 ethers in concentrations from about 1 to 20 volume percent, so that the combined alcohol and cosolvent concentration in the composition is not more than 30 volume percent.
  • This fuel composition would be combined with about 0.004 to 0.264 grams manganese of MMT per litre (about 1/64 to 1 gram manganese of MMT per gallon) of the composition with about 1 to about 40 volume percent aromatic hydrocarbons in the composition together with an unleaded gasoline base.
  • a more desirable composition would contain aromatic hydrocarbons from about 1 to about 20 volume percent together with MMT from about 0.004 to about 0.066 grams manganese per litre (about 1/64 to about 1/4 grams manganese per gallon) of composition.
  • a preferred composition would contain aromatic hydrocarbons from about 1 to 10 volume percent together with MMT from about 0.004 to 0.033 grams manganese per litre (about 1/64 to about 1 / 8 grams manganese per gallon) of the composition.
  • An even more preferred composition would contain aromatic hydrocarbons in a concentration range up to about 6 volume percent of the composition.
  • Another desirable fuel composition contains methanol from about 1 to about 15 volume percent of the composition, C 2 to C 12 aliphatic alcohols, C 2 - C 12 ethers and/or C 3 -C 12 ketones in concentration from about 1 to about 15 volume percent of the composition and a MMT concentration from about 0.004 to about 0.132 gram of manganese per litre (about 1/64 to about 1/2 gram of manganese per gallon) of fuel composition together with about 1.0 to about 20 volume percent aromatic hydrocarbons.
  • a preferred MMT concentration would be from about 0.004 to about 0.066 grams manganese per litre (about 1/64 to about 1/4 grams manganese per gallon) of the composition together with about 1.0 to about 10 volume percent aromatic hydrocarbons.
  • a more preferred MMT concentration would be from about 0.004 to 0.033 grams manganese per litre (about 1/64 to about 1/8 grams manganese per gallon) of the fuel composition with about 1.0 to about 5 volume percent aromatic hydrocarbons.
  • a preferred fuel composition contains methanol from about 1 percent to about 9 volume percent of the composition, C 2 to C 12 aliphatic alcohols in concentrations from about 1 to about 10 volume percent of the composition, a MMT concentration from about 0.004 to about 0.066 gram manganese per litre (1/64 to about 114 gram manganese per gallon) of fuel composition with aromatic hydrocarbons from about 1.0 to about 20 volume percent and a more preferred MMT concentration from about 0.008 to 0.033 gram per litre (about 1/32 to about 1/8 gram per gallon) with aromatic hydrocarbons from about 1.0 to about 10 volume percent of the fuel composition.
  • a more preferred fuel composition contains methanol from about 2 to about 6 volume percent with C 2 to C 12 saturated aliphatic alcohols in concentration from about 1 percent to about 10 volume percent of the composition and a MMT concentration from about 0.004 to 0.066 gram manganese per litre (about 1/64 to about 1/4 gram manganese per gallon) of fuel composition together with about 1.0 to about 20 percent aromatic hydrocarbons in the composition and an even more preferred MMT concentration is from about 0.004 to 0.033 gram per litre (about 1/64 to 1/8 gram per gallon) together with about 1.0 to about 10 volume percent aromatic hydrocarbons in the composition.
  • Another highly preferred fuel composition would contain methanol from about 2 to 6 volume percent with C 4 to C 12 saturated aliphatic alcohols in concentrations from about 1 percent to about 10 volume percent of the composition, particularly those having boiling points higher than tertiary butanol and a MMT concentration from about 0.004 to about 0.066 grams manganese per litre (about 1/64 to about 1/4 grams manganese per gallon) of fuel composition together with about 1.0 to about 20 percent aromatic hydrocarbons in the composition.
  • a more preferred MMT concentration would be from about 0.004 to 0.033 gram per litre (about 1/64 to about 1/8 gram per gallon) together with about 1.0 to about 10 volume percent aromatic hydrocarbons in the composition.
  • Aromatic hydrocarbons often are the resultant product of the reformer, Fluid Catalyst Cracker Unit (FCC), Riser Cracker Unit or Coker Unit using napthas, gas oils, resid, coal liquids, shale oils, asphalt and/or other similar feed stocks.
  • Aromatic hydrocarbons may also be the product of other reaction processing units within a petrochemical complex or refinery. These aromatic hydrocarbons may be streams themselves.
  • Applicant's contemplated aromatic hydrocarbons include reformates, raffinates, platformates, alkalates, napthas, distillates, isomerates, polymerates, light cycle oils, coal liquids, biomass liquids, wood liquids and the like.
  • aromatic hydrocarbons or aromatic based hydrocarbon streams normally boil in ranges which include temperatures inside and/or outside normal gasoline boiling temperatures. They often are components of streams which themselves can not readily be added to gasoline or streams which can not be economically processed into gasoline for various reasons. Often these streams contain significant quantities of olefins and paraffins. Higher octane components are preferred, especially branched chain, condensed ring and iso-paraffins and olefins. In certain cases these streams are exclusive of aromatic hydrocarbons.
  • light cycle oils which are generally known to be fluid catalytic cracker (FCC) recycle oils and which are produced by the FCC from heavy gas oils, have boiling ranges normally varying from about 150° C (300 F) to about 340" C (650" F) and in certain cases boiling at temperatures outside these ranges.
  • Light cycle oils are generally recycled through the FCC to produce additional gasoline material until the economics of recycling diminish and they become a component of distillate, diesel fuel oils, or other fuels.
  • Acceptable aromatic hydrocarbons are those having boiling ranges from approximately 90 C (200 F) to 370 C (700 F) and in certain cases boiling temperatures outside these ranges.
  • Applicant's aromatic hydrocarbons, or streams or fractions containing aromatic hydrocarbons thereof are those with a carbon molecular content up to generally C-25, more preferred are those up to C-15, with the most preferred being those between C-5 to C-15.
  • Applicant's aromatic hydrocarbons can be added to or processed into gasoline only at additional expense to the refiner because of the nature of the process stream itself. Often this additional expense if prohibitive.
  • Figure 1 shows that the "uncorrected base fuel”, (an alcohol gasoline composition without the balance of Applicant's MMT and aromatic hydrocarbon ingredients), has the expected initial and mid-range distillation fraction depression when compared to the base gasoline. Note that the "corrected fuel” (containing Applicant's defined ingredients) substantially improves the initial and mid-range distillation depression as well as improving the end boiling point characteristics of the "uncorrected base fuel with aromatic hydrocarbons” (without the benefit of Applicant's other ingredients).
  • aromatic based hydrocarbon streams or fractions thereof are acceptable.
  • generally acceptable aromatic hydrocarbons streams are those which have at least 10% by weight aromatic hydrocarbons, but those having an aromatic content in excess of 50% or more by weight are more preferred.
  • the hydrocarbon streams or fractions thereof have an octane (R + M)/2 rating in excess of 50, a more preferred octane rating would be in excess of 70, an even more preferred octane rating would be in excess of 85 (generally, the higher the octane rating the better).
  • the initial lighter, lower boiling point hydrocarbon based fractions boiling between 90 °C (200 F) to 230 C (450 F) are preferred over those fractions boiling between 90° C (200 F) to 290 C (550 F) over those fractions boiling from 90° C (200° F) to 370 C (700° F).
  • aromatic hydrocarbons which are typically found in normal boiling range gasolines it is also within the scope and teachings of this invention to utilize aromatic hydrocarbons streams or fractions thereof and/or any other aromatic based hydrocarbon streams or fractions thereof which would not normally be used in normal boiling range gasolines in significant quantities, if any. It is within the teachings and scope of this invention to substitute an individual aromatic hydrocarbon with other aromatic hydrocarbons, with aromatic hydrocarbon streams or fractions thereof, with aromatic based hydrocarbon streams or fractions thereof. Aromatic hydrocarbon substitution may also be made with acceptable non-aromatic hydrocarbon streams or fractions thereof.
  • aromatic hydrocarbon streams or fractions thereof may be the product of isomerization units, crude distillation units, cokers, vacuum distillation units, hydrocracking units, catalytic cracking units, riser cracking units, reforming units, akylation units, polymerization units, hydrodesulfurization units, pyrolsis units, gasification units and the like, and/or produced from any combination of these units using crude oil, natural gasolines, natural gas, natural gas liquids, heavy gas oils, coal, coal liquids, shale oil, biomass, wood, lignate, peat moss, tar sands and the like, at a refinery, petrochemical complex and/or other production complex.
  • volume percentages of aromatic hydrocarbons up to 45% as taught in the Table of Ingredient Ranges and elsewhere in this invention are in addition to the aromatic content percentage of the unleaded gasoline bases as taught in Section 6 below.
  • Applicant contemplates that it may be necessary in certain circumstances to tailor the boiling characters and the distillation characteristics of these aromatic hydrocarbon streams or fractions thereof. Tailoring, for example, may include cutting the aromatic hydrocarbon so that its ending boiling point would be between 200 C (400 F) to about 290 C (550° F). This may be desirable in order to conform to Applicant's blended fuel with ASTM D 439 standards. In certain instances it may be desirable to separate one or more components within the aromatic based hydrocarbon stream from other components of the stream. Other tailoring would include mixing various noncut or cut aromatic hydrocarbon fractions together.
  • Applicant's invention Applicants can effectively improve the end boiling point and emission characteristics of the fuel composition which would normally be expected by the addition of the contemplated aromatic hydrocarbon. Applicant's may also control distillation depression and increased RVP which would normally occur with the addition of lower molecular weight alcohols. Applicant also corrects the excessive hydrocarbon emissions occurring with the addition of MMT to unleaded gasoline. These attributes of Applicant's invention represent a very significant departure from the prior art and in view of the prior art literature is quite unexpected and novel.
  • Figure 2 illustrates the range of hydrocarbon emissions on the basis of engine out hydrocarbons (EOHC) improvement expected at 8000 kms (5,000 miles) using the defined proportions of C, to C 6 aliphatic alcohols (cosolvents), MMT, aromatic hydrocarbons and unleaded base gasolines (the "Corrected Fuels"), over fuels just employing MMT concentrations, without the benefit of C 1 to C 6 aliphatic alcohols and aromatic hydrocarbons (the "Uncorrected Fuels”).
  • EOHC engine out hydrocarbons
  • Figure 2 illustrates the significant differences in the hydrocarbon emission behavior of pre-1980 standard model cars (manufactured for under 0.93 grams of hydrocarbon emission per kilometer (1.5 grams per mile) USA standards) using the "Uncorrected Fuels” and "Corrected Fuels” formulated in accordance with Applicant's invention.
  • the preferred cyclomatic manganese tricarbonyl used in our composition is methyl cyclopentadienyl manganese tricarbonyl (MMT) but the composition can contain a homologue or such other substituents as, for example, alkenyl, aralkyl, aralkenyl, cycloalkyi, cycloalkenyl, aryl and alkenyl groups.
  • MMT methyl cyclopentadienyl manganese tricarbonyl
  • cyclopentadienyl manganese tricarbonyl antiknock compounds are: cyclopentadienyl manganese tricarbonyl; methylcyclopentadienyl manganese ben- zyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3-cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2-diphenylcyclopentadienyl manganese tricarbonyl; 3-propenylienyl manganese tricarbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl manganese tricarbonyl; 2.3.4.7 - propyflourentyl manganese tricarbonyl; 3-naphthylfluorenyl manganese tricarbonyl; 4.5.6.7 - tetrahydroindenyl manganese tricarbonyl; 3-e
  • concentrations of the methyl cyclomatic manganese tricarbonyl compound concentrations (expressed as grams of manganese metal per gallon of the resulting fuel composition) as low as 0.004 grams manganese per litre (1/64 grams manganese per gallon) are sufficient in many cases.
  • concentrations up to and including 0.264 grams manganese per litre (1.0 grams manganese per gallon) can be employed, but are less preferred.
  • amounts outside of the above-recited range can also be employed, but such concentrations tend to be less satisfactory.
  • concentrations of cyclomatic manganese tricarbonyl in the range of from about 0.004 grams to about 0.066 grams manganese/litre (about 1/64 grams to about 1;4 grams manganese-gallon) give good results, and concentrations from 0.004 to 0.033 grams manganese litre (1 64 to 1.8 grams manganese/gallon) give better results and are preferred.
  • This invention also contemplates the use of other additives, such as gum and corrosion inhibitors, multipurpose additives and scavengers, made necessary or desirable to maintain fuel system cleanliness and control exhaust emissions due to the presence of alcohol, organo-manganese compounds and aromatic hydrocarbons in the fuel. The methods of incorporation of such additives into fuel blends are well known to the art.
  • a cosolvent should also be employed to insure phase stability of the fuel composition to the extent that the fuel composition containing methanol and approximately 500 parts per million water will not phase separate at -9.7 C (15° F), or the lowest probable temperature to which the fuel composition will be exposed.
  • the methanol to cosolvent ratio should not exceed about 5 parts methanol to 1 part cosolvent depending upon the nature of the base fuel and the cosolvent(s) used. There does not appear to be any minimum ratio of methanol to cosolvent, except as required by economics or the desired performance characteristics of the fuel composition. In certain cases if the amount of methanol used is about 5 percent by volume or less of the fuel composition, cosolvents may not be required. However, it is good practice to use cosolvents whenever methanol is employed.
  • the cosolvent(s) can be selected from the group consisting of C 2 to C, 2 aliphatic alcohols, C 3 to C1 2 ketones and/or C 2 to C 12 ethers. Within the scope of this invention it is contemplated that these cosolvents may also be used with any C, - C 6 aliphatic alcohol, especially in cases where corrosion, phase stability or vapor pressure become an issue. It is also within the scope and teaching of this invention to employ one or more alcohols, ketones or ethers within a particular class of cosolvents and/or to employ any one or more cosolvents classes of this invention simultaneously.
  • mixed cosolvents including mixed alcohols, ethers and/or ketones
  • mixed cosolvent alcohols particularly those in the C 2 to C s range have a particularly ameleorative effect on both RVP and octane blending values.
  • cosolvent class rankings would be alcohols first, ketones second, and ethers last. Also, the higher the average boiling point of the cosolvents employed within a particular class, up to a C 8 cosolvent, the greater the preference. With cosolvents greater than C 8 the reference is reversed so that a C 9 cosolvent would be preferred over a C 10 cosolvent and so forth.
  • the alcohol cosolvents will have from two to twelve carbon atoms.
  • the preferred cosolvent alcohols are saturates having high water tolerances and high boiling points.
  • Representative alcohol cosolvents include ethanol, isopropanol, n-propanol, tertiary butanol, 2-butanol, isobutanol, n-butanol, pentanols, amyl alcohol, cyclohexanol, 2-ethylhexanol, furfuryl alcohol, iso amyl alcohol, methyl amyl alcohol, tetrahydrofurfuryl alcohol, hexanols, cyclohexanols, septanols, octanols and the like.
  • the alcohol cosolvents in reverse order of their preference, are propanols, butanols, pentanols, hexanols and the other higher boiling point alcohols.
  • the more preferred alcohol cosolvents include isobutanol, n-butanol, pentanol and the other higher boiling point alcohols.
  • ketones used as cosolvents in fuel compositions taught herein will have from three to about twelve carbon atoms.
  • Lower alkenyl ketones are, however, slightly preferred.
  • Representative lower alkenyl ketones would include diethyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, ethyl butyl ketone, butyl isobutyl ketone and ethyl propyl ketone and the like.
  • ketones include acetone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl isamyl ketone, methyl propyl ketone and the like.
  • a representative cyclic ketone would be ethyl phenyl ketone.
  • Representative ethers which can be used as cosolvents in fuel compositions taught herein will have from 2 to about 12 carbon atoms and would include the preferred methyl alkyl t-butyl ethers such as methyl tert-butyl ether, ethyl tertiary butyl ether, also preferred tertiary amyl methyl ether, dialkyl ether, isopropyl ether, diisopropyl ether, diethyl ether, ethyl n-butyl ether, ethylidenedimethyl ether, butyl ether, and ethylene glycol dibutyl ether and the like.
  • the representative straight ethers which can be used in the fuel blends of this invention would include straight chain ethers such as those presented above, as well as cyclic ethers wherein the ether's oxygen molecule is in a ring with carbon atoms.
  • straight chain ethers such as those presented above, as well as cyclic ethers wherein the ether's oxygen molecule is in a ring with carbon atoms.
  • tetrahydrofurans such as, for example, 2-methyltetrahydrofuran, 2-ethyltetrahydrofuran, and 3-methyletetrahydrofuran may also find use in the present invention.
  • the most preferred ether would be a branch chained ether.
  • the above ethers should also be readily soluble, either directly or indirectly in gasoline.
  • the preferred methanol/cosolvent ratio will range from 0.2 to 3 parts methanol to 1 part cosolvent. Ratios from about 3 to 5 parts methanol to 1 part cosolvent are also preferred in certain circumstances.
  • the ratio of methanol to cosolvent can exceed 5 to 1 or be less than 0.5 to 1. However methanol/cosolvent ratios outside these ranges are normally less desirable unless vapor pressure or technical enleanment are issues in the fuel formulation.
  • the methanol to cosolvent ratios will generally be higher when a higher boiling point aliphatic alcohol up to C8 is the cosolvent and lowest when ethanol is the cosolvent.
  • methanol to cosolvent ratios are higher with alcohols, than they are with ketones, than they are with ethers. That is to say, when a comparable higher boiling point or molecular weight alcohol, ketone or ether is compared, the highest ratio (within the general range of 3 to 5 parts methanol to 1 part cosolvent) is permissible when the cosolvent is an alcohol, the second highest ratio when the cosolvent is the ketone and the lowest ratio when the cosolvent is an ether.
  • the preferred ratios might be 3 to 5 parts methanol to 1 part N-butanol, 1 to 2 parts methanol to 1 part methyl ethyl ketone, and 1 part methanol to 2 to 3 parts diethyl ether.
  • the methanol-cosolvent ratios should be at their highest when higher molecular weight cosolvent molecules (e.g., C 4 - C 12 ) are used.
  • a less desirable base gasoline with lower percentages of aromatic components generally will require, for example, a lower methanol to cosolvent ratio and a higher average boiling point alcohol and cosolvent components.
  • This same low aromatic gasoline will limit the flexibility of reducing or increasing the total volume of the alcohol component. It is likely that the alcohol component as a percent of volume would be easier to increase then it would be to decrease.
  • a methanol to cosolvent ratio of 3 to 1 using isopropanol as the cosolvent, together with the alcohol component representing 7 percent by volume of the fuel would normally be acceptable if the fuel were to be distributed in a dry system averaging 16°C (60 F). However, if it were anticipated that the fuel would be exposed to -7° C (20 F) temperatures, or to greater concentrations of moisture or water, then certain adjustments would have to be made. One or more of the following adjustments would be required:
  • the age of the vehicular population which consumes the finished fuel also impacts the amount of oxygen which may be contained in the fuel.
  • the finished fuel may contain upwards to 5-7 percent total oxygen by weight.
  • Those newer automobiles using 3-way catalysts which require more stringent air fuel ratios are limited to generally 4-5 percent total oxygen by weight.
  • New vehicles containing oxygen sensing devices may use fuels containing upwards of 7 percent oxygen by weight. With the anticipated improvements of oxygen sensing devices in 1985 and future model years, the oxygen content of the finished fuel could approach 12 percent or more by weight.
  • Another element that must be considered when formulating the cosolvent component is the cosolvent's effect with the aromatic hydrocarbon component on mid and end range distillation temperatures.
  • C 2 - C4- alcohols up to and including TBA
  • C 4 - (higher than TBA) - C12 alcohols tend to reduce temperatures beyond the mid-range.
  • the inclusion of aromatic hydrocarbons into the fuel composition raises end range temperatures and tends to compress the distillation curve with the effect of increasing mid-range temperatures. Therefore, effect must be given to the particular characteristics of the aromatic hydrocarbon component (i.e., boiling range, end boiling point and the like) when formulating the cosolvent component.
  • Aromatic hydrocarbon use in gasoline will generally represent an attractive and economic utilization for the refinery. However, since the use of lower molecular weight alcohols generally increases RVP, the refinery must generally back out inexpensive butanes from the gasoline composition to reduce this RVP increase.
  • gasoline to which this invention is applied is a lead fuel or substantially lead free gasoline.
  • the gasoline bases in Applicants' fuel composition are conventional motor fuels boiling in the general range of about 20 C (70°) to about 230 C (440 F). They include substantially all grades of unleaded gasoline presently being employed in spark ignition internal combustion engines. Generally they contain both straight runs and cracked stock, with or without alkylated hydrocarbons, reformed hydrocarbons and the like.
  • Such gasolines can be prepared from saturated hydrocarbons, e.g., straight stocks, alkylation products and the like, with detergents, antioxidants, dispersants, metal deactivators, rust inhibitors, multi-functional additives, demulsifiers, fluidizer oils, anti-icing, combustion catalysts, corrosion and gum inhibitors, emulsifiers, surfactants, solvents and/or other similar or known additives. It is contemplated that in certain circumstances these additives may be included in concentrations above normal levels made necessary to accommodate the ingredients of Applicant's invention.
  • 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 4 olefins and butanes using an acid catalyst such as sulfuric acid or hydrofluoric acid, and aromatics made from a reformer.
  • the olefins are generally formed by using such procedures as thermal cracking and catalytic cracking. Deyhydrogenation of paraffins to olefins can supplement the gaseous olefins occurring in the refinery to produce feed material for either polymerization or alkylation processes.
  • the saturated gasoline components comprise paraffins and naphthenates. These saturates are 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.
  • gasoline bases are those having an octane rating of (R + M)/2 ranging from 78-95. It is desirable to blend the gasoline base as contemplated in Applicant's invention so that the minimum aromatic content within a normal gasoline base, to which the balance of Applicant's ingredients are added to, is no less than 5% and preferably greater than 20%. This minimum aromatic content of the base gasoline may be generated and introduced into the gasoline as a compliment to or as a result of the process stream(s) or fractions thereof which are taught as necessary hydrocarbon ingredients of this invention.
  • the gasoline base should have an olefinic content ranging from 1% to 30%, and a saturate hydrocarbon content ranging from about 40 to 80 volume percent.
  • the motor gasoline bases used in formulating the fuel blends of this invention generally are within the parameters of ASTM D-439 and have initial boiling points ranging from about 20 C (70 F) to about 45 C (115°F) and final boiling points ranging from about 190°C (380 F) to about 230 C (440 F) as measured by the standard ASTM distillation procedure (ASTM D-86). Intermediate gasoline fractions boil away at temperatures within these extremes.
  • desirable base gasoline compositions would include as many aromatics with C 8 or lower carbon molecules as possible in the circumstances.
  • the ranking or aromatics in order of their preference would be: benzene, toluene, m-xylene, ethylbenzene, o-xylene, isoproplydenzene, N-propybenzene and the like.
  • the next preferred gasoline component in terms of phase stability would be olefins.
  • the ranking of preferred olefins in order of their preference would be; 2-methyl-2-butane, 2 methyl-1 butane, 1 pentent, and the like.
  • olefinic content must be closely watched.
  • the least preferred gasoline component in terms of phase stability would be paraffins.
  • the ranking of preferred paraffins in order of their preference would be; cyclopentane, N-pentane, 2,3 dimethylbutane, isohexane, 3-methylpentane and the like.
  • aromatics are generally preferred over olefins and olefins are preferred over paraffins.
  • olefins are preferred over paraffins.
  • the lower molecular weight components are preferred over the higher molecular weight components.
  • base gasolines having a low sulfur content as the oxides of sulfur tend to contribute to the irritating and choking characteristics of smog and other forms of atmospheric pollution.
  • the base gasolines should contain not more than 0.1 weight percent of sulfur in the form of conventional sulfur-containing impurities. Fuels in which the sulfur content is no more than about 0.02 weight percent are especially preferred for use in this invention.
  • the gasoline bases of this invention can also contain other high octane organic blending agents.
  • Nonlimiting examples include phenols (e.g., P-cresal, 2, 4 xylenal, 3-methoxyphenal), esters (e.g., isopropyl acetate, ethyl acrylate) oxides (e.g., 2-methylfuran), ketones (e.g., acetone, cyclopentanone), alcohols (furon, furfuryl), ethers (e.g., MTBE, TAME, dimethyl, diisopropyl), aldehydes and the like.
  • phenols e.g., P-cresal, 2, 4 xylenal, 3-methoxyphenal
  • esters e.g., isopropyl acetate, ethyl acrylate
  • oxides e.g., 2-methylfuran
  • ketones e.g., acetone, cyclopent
  • the gasoline bases which this invention employs should be lead-free or substantially lead-free.
  • the gasoline may contain antiknock quantities of other agents such as cyclopentadienyl nickel nitrosyl, N-methyl aniline, and the like. Antiknock promoters such as 2.4 pentanedione may also be included.
  • the descriptive characteristics of one common base gasoline is given as example 2. Obviously many other standard and specialized gasolines can be used in Applicants' fuel blend.
  • the fuel composition of this invention can generally be prepared by adding the cyclopentadienyl manganese antiknock compound, the C, to C 6 alcohols and the cosolvents, if any, together with aromatic hydrocarbons together with the base gasoline with sufficient agitation to give a uniform composition to the finished fuel. It is essential in the practice of this invention only that the novel combination of additives, a cyclopentadienyl manganese tricarbonyl and the C 1 to C 6 alcohols and cosolvents, if any, along with aromatic hydrocarbons be present in the defined-proportions with unleaded gasoline bases immediately prior to vaporization and combustion of the fuel in the engine. Accordingly, it is within the scope of this invention to add the components of the composition as herein taught either separately in any sequence, or as a mixture with each other, so long as the foregoing requirement is met.

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Claims (24)

1. Composition de carburant pour contrôler les émissions d'hydrocarbures d'un moteur à combustion interne à allumage par étincelle, comprenant un mélange :
d'une base d'essence sans plomb formée d'hydrocarbures représentant environ 70 à 99 % en volume de la composition de carburant;
un composé antidétonant de cyclopentadiényl manganèse tricarbonyle ayant une concentration en manganèse d'environ 0,000264 à environ 0,264 g de manganèse par litre de la composition de carburant; et
au moins un solvant choisi dans le groupe comprenant les alcools aliphatiques en Ci à C6 en une concentration d'environ 1,0 à environ 30,0 % en volume de la composition de carburant.
2. Composition de carburant suivant la revendication 1, caractérisée en ce qu'elle comprend de plus au moins un cosolvant choisi dans le groupe comprenant les alcools en C7-C12, les cétones en C3-C12 et les éthers en C2-C12.
3. Composition de carburant suivant la revendication 1, caractérisée en ce qu'elle comprend de plus un hydrocarbure aromatique lourd, y compris ses coulées, fractions et mélange, et un moyen pour améliorer la conduisabilité.
4. Composition de carburant suivant la revendication 3, caractérisée en ce qu'elle comprend de plus au moins un cosolvant choisi dans le groupe comprenant les alcools aliphatiques en C7 à C12 les cétones en C3 à Ci et les éthers en C2 à C12, et un moyen pour modifier les températures d'ébullition de telle sorte que la composition de carburant bout dans les intervalles des essences.
5. Composition de carburant suivant la revendication 4, caractérisée en ce que le solvant et le cosolvant constituent ensemble une concentration d'environ 1,0 à environ 30,0 % en volume de la composition de carburant.
6. Composition de carburant pour contrôler les émissions d'hydrocarbures d'un moteur à combustion interne à allumage par étincelle, comprenant un mélange :
d'une base d'essence formée d'hydrocarbures bouillant dans l'intervalle des essences, représentant environ 76 à 99 % en volume de la composition de carburant;
d'un composé antidétonant de cyclopentadiényl manganèse tricarbonyle ayant une concentration en manganèse d'environ 0,000264 à environ 0,264 g de manganèse par litre de la composition de carburant; et
de méthanol en une concentration d'environ 0,2 à environ 24,0 % en volume de la composition de carburant.
7. Composition de carburant suivant la revendication 6, caractérisée en ce qu'elle comprend de plus au moins un cosolvant choisi dans le groupe comprenant les alcools aliphatiques en C2 à C12, les cétones en C3 à C12 et les éthers en C2 à CI 2, en une concentration d'environ 1,0 à environ 20,0 % en volume de la composition de carburant.
8. Composition de carburant suivant la revendication 6, caractérisée en ce qu'elle comprend de plus un hydrocarbure aromatique lourd, y compris ses fractions, coulées et mélange, choisi dans le groupe comprenant les hydrocarbures en C5 à C2S.
9. Composition de carburant suivant la revendication 8, caractérisée en ce qu'elle comprend de plus au moins un cosolvant choisi dans le groupe comprenant les alcools en C2 à C12, les cétones en C3 à C12 et les éthers en C2 à C13, et un moyen pour modifier les températures d'ébullition de la composition de carburant.
10. Procédé pour réduire les émissions d'hydrocarbures d'échappement d'un moteur à combustion interne allumé par étincelle et d'un système d'échappement conçu pour des carburants sans plomb, ce procédé comprenant :
le mélange d'une base d'essence sans plomb formée d'hydrocarbures bouillant dans l'intervalle des essences représentant environ 70 à environ 99 % en volume de la composition de carburant avec :
un composé antidétonant de manganèse tricarbonyle cyclomatique ayant une concentration en manganèse d'environ 0,000264 à environ 0,264 g de manganèse par litre de la composition de carburant; et
au moins un solvant choisi dans le groupe comprenant les alcools aliphatiques en Ci à C3 en une concentration d'environ 1,0 à environ 30,0 % en volume de la composition de carburant; et
l'apport et la combustion de la composition de carburant résultante dans le moteur à combustion interne allumé par étincelle et l'émission des émissions résultantes par le système d'échappement.
11. Procédé suivant la revendication 10, caractérisé en ce que la composition comprend de plus un hydrocarbure aromatique lourd, du groupe des hydrocarbures aromatiques, y compris ses coulées, fractions et mélange, dans la gamme des hydrocarbures en C5 à C2S.
12. Procédé suivant l'une ou l'autre des revendications 10 et 11, caractérisé en ce que la composition comprend de plus au moins un cosolvant choisi dans le groupe comprenant les alcools en C4 à C12, les éthers en C2 à C12 et les cétones en C3 à C12.
13. Procédé suivant l'une quelconque des revendications 10 à 12, caractérisé en ce que le manganèse tricarbonyle cyclomatique est du cyclopentadiényl manganèse tricarbonyle en une concentration d'environ 0,000264 à environ 0,132 g par litre de composition de carburant.
14. Procédé suivant l'une quelconque des revendications 10 à 13, caractérisé en ce que le système d'échappement est un convertisseur catalytique.
15. Procédé pour améliorer la conduisabilité de compositions d'alcool de poids moléculaire inférieur/essence dans un moteur à combustion interne allumé par étincelle, ce procédé comprenant :
le mélange d'une base d'essence formée d'hydrocarbures bouillant l'intervalle des essences avec :
un composé antidétonant de manganèse tricarbonyle cyclomatique ayant une concentration en manganèse d'environ 0,000264 à environ 0,264 g de manganèse par litre de la composition de carburant,
au moins un solvant choisi dans le groupe comprenant le méthanol et l'éthanol,
au moins un cosolvant choisi dans le groupe comprenant les alcools aliphatiques en C3 à C12, les cétones en C3 à C12 et les éthers en C2 à C12, et
un moyen pour modifier les températures d'ébullition de la composition de carburant pour améliorer la distillation; et
l'apport et la combustion de la composition de carburant résultante dans le moteur à combustion interne allumé par étincelle.
16. Procédé suivant la revendication 15, caractérisé en ce que la composition de carburant comprend de plus un hydrocarbure aromatique lourd, y compris ses coulées, fractions et mélanges, choisi dans le groupe comprenant les hydrocarbures en Cs à C25.
17. Procédé suivant la revendication 15, caractérise en ce que la composition de carburant comprend du méthanol en une concentration d'environ 1,0 à environ 15,0 % en volume de la composition de carburant, au moins un cosolvant choisi dans le groupe comprenant les alcools aliphatiques en C2 à C12, en une concentration d'environ 1,0 à environ 15,0 % en volume de la composition de carburant, du cyclopentadiényl manganèse tricarbonyle en une concentration d'environ 0,004 à environ 0,132 g de manganèse par litre de composition de carburant et, en combinaison, un composant hydrocarboné aromatique lourd en une concentration d'environ 1,0 à environ 45,0 % en volume de la composition de carburant et un moyen pour modifier la température d'ébullition de la composition de carburant jusque dans les intervalles des essences.
18. Procédé suivant la revendication 15, caractérisé en ce que le cosolvant a un point d'ébullition moyen supérieur au butanol tertiaire.
19. Procédé suivant la revendication 15, caractérisé en ce que le moteur à combustion interne allumé par étincelle est conçu pour un usage sans plomb et comprend de plus un système d'échappement du type convertisseur catalytique.
20. Procédé d'utilisation d'un hydrocarbure aromatique lourd bouillant à des températures au-dessus des intervalles des essences dans un moteur à combustion interne allumé par étincelle nécessitant des intervalles de températures des essences, ce procédé comprenant :
le mélange d'une base d'essence formée d'hydrocarbures en combinaison avec :
au moins un solvant choisi dans le groupe comprenant les alcools aliphatiques en Ci à C6, et éventuellement,
au moins un cosolvant choisi dans le groupe comprenant les alcools aliphatiques en C7 à Ci2, les cétones en C3 à C12 et les éthers en C2 à Ci2, et
en combinaison, un hydrocarbure aromatique lourd, du groupe des hydrocarbures de base aromatique lourde, y compris ses coulées, fractions et mélanges, qui en tout ou en partie bouillent au-dessus des intervalles des essences, et un moyen pour réduire les températures d'ébullition de manière à bouillir dans les intervalles des essences; et
l'apport et la combustion de la composition de carburant résultante dans le moteur à combustion interne allumé par étincelle.
21. Procédé suivant la revendication 20, caractérisé en ce que le solvant et l'éventuel cosolvant peuvent former un azéotrope, notamment des azéotropes multiples, avec l'hydrocarbure aromatique lourd.
22. Procédé suivant la revendication 20, caractérisé en ce que la composition de carburant comprend la base d'essence à raison d'environ 25,0 à environ 98,0 % en volume de la composition de carburant, le solvant à raison d'environ 1,0 à environ 30,0 % en volume de la composition de carburant, le cosolvant à raison d'environ 1,0 à environ 20,0 % en volume de la composition de carburant, de telle sorte que la quantite totale de solvant et de cosolvant, ensemble, n'excède pas 30,0 % en volume de la composition de carburant, et l'hydrocarbure aromatique lourd à raison d'environ 1,0 à environ 45,0 % en volume de la composition de carburant.
23. Procédé suivant la revendication 20, caractérisé en ce que la composition de carburant est sans plomb et comprend de plus un composé antidétonant de cyclopentadiényl manganèse tricarbonyle en une concentration d'environ 0,000264 à environ 0,264 g de manganèse par litre de composition de carburant, le moteur à combustion interne allumé par étincelle étant conçu pour des carburants sans plomb et comprenant de plus un système d'échappement du type convertisseur catalytique.
24. Procédé suivant la revendication 20, caractérisé en ce que le solvant ou son mélange est choisi dans le groupe comprenant le méthanol, l'éthanol, le n-propanol et l'isopropanol et le cosolvant ou son mélange est choisi dans le groupe comprenant les alcools aliphatiques en C4 à Ci2.
EP86906042A 1985-08-28 1986-08-26 Composition de carburant sans plomb Expired - Lifetime EP0235280B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86906042T ATE69462T1 (de) 1985-08-28 1986-08-26 Bleifreie brennstoffzusammensetzung.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US77083685A 1985-08-28 1985-08-28
US770836 1985-08-28
PCT/US1986/001757 WO1987001384A1 (fr) 1985-08-28 1986-08-26 Composition de carburant sans plomb

Publications (4)

Publication Number Publication Date
EP0235280A1 EP0235280A1 (fr) 1987-09-09
EP0235280A4 EP0235280A4 (fr) 1988-01-07
EP0235280B1 true EP0235280B1 (fr) 1991-11-13
EP0235280B2 EP0235280B2 (fr) 1999-06-23

Family

ID=25089843

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86906042A Expired - Lifetime EP0235280B2 (fr) 1985-08-28 1986-08-26 Composition de carburant sans plomb

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EP (1) EP0235280B2 (fr)
AT (1) ATE69462T1 (fr)
AU (1) AU6377586A (fr)
CA (1) CA1310832C (fr)
DE (1) DE3682503D1 (fr)
WO (1) WO1987001384A1 (fr)

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WO2013043220A1 (fr) * 2011-09-23 2013-03-28 Butamax (Tm) Advanced Biofuels Llc Procédé pour la production d'essence en utilisant du butanol dans le stock d'essence

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CA2076302C (fr) * 1991-08-23 2003-05-27 Thomas Albert Leeper Carburants a proprietes ameliorees
JPH08504839A (ja) * 1992-03-04 1996-05-28 シェパード クリスチーン メアリー 強化炭化水素並びにその製造方法及び使用方法
US5551957A (en) * 1992-05-06 1996-09-03 Ethyl Corporation Compostions for control of induction system deposits
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US5511517A (en) * 1994-02-10 1996-04-30 Ethyl Corporation Reducing exhaust emissions from otto-cycle engines
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CN1150447A (zh) * 1994-03-02 1997-05-21 威廉·C·奥尔 无铅mmt燃料组合物
EP0763079A1 (fr) * 1994-05-31 1997-03-19 ORR, William C. Procedes et compositions pour combustion en phase vapeur
WO1996040844A1 (fr) * 1995-06-07 1996-12-19 Orr William C Procede de combustion en phase vapeur et compositions ii
JP3948796B2 (ja) * 1997-09-30 2007-07-25 新日本石油株式会社 筒内直接噴射式ガソリンエンジン用無鉛ガソリン
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US10081774B2 (en) 2011-09-23 2018-09-25 Butamax Advanced Biofuels Llc Systems and processes for production of fuel and fuel blends

Also Published As

Publication number Publication date
DE3682503D1 (de) 1991-12-19
ATE69462T1 (de) 1991-11-15
EP0235280A1 (fr) 1987-09-09
EP0235280A4 (fr) 1988-01-07
WO1987001384A1 (fr) 1987-03-12
AU6377586A (en) 1987-03-24
CA1310832C (fr) 1992-12-01
EP0235280B2 (fr) 1999-06-23

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