EP0656045A1 - Composition de carburant sans plomb a base de mmt - Google Patents

Composition de carburant sans plomb a base de mmt

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Publication number
EP0656045A1
EP0656045A1 EP93920308A EP93920308A EP0656045A1 EP 0656045 A1 EP0656045 A1 EP 0656045A1 EP 93920308 A EP93920308 A EP 93920308A EP 93920308 A EP93920308 A EP 93920308A EP 0656045 A1 EP0656045 A1 EP 0656045A1
Authority
EP
European Patent Office
Prior art keywords
fuel
manganese
emissions
combustion
composition
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.)
Pending
Application number
EP93920308A
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German (de)
English (en)
Inventor
William C. Orr
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Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0656045A1 publication Critical patent/EP0656045A1/fr
Pending legal-status Critical Current

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    • 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
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    • C10L1/14—Organic compounds
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    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
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    • C10L1/14—Organic compounds
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
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    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
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Definitions

  • This invention relates generally to novel unleaded fuel compositions for spark ignition internal combustion engines. More particularly, it relates to organomanganese and unleaded fuel combinations, and a mechanical and/or chemical means capable of reducing the formation of heavy manganese oxides (e.g. Mn 3 0 4 ) during combustion, such that resultant hydrocarbon emissions can meet minimal legal environmental standards.
  • heavy manganese oxides e.g. Mn 3 0 4
  • organo-metallic compounds as antiknock agents in fuels for high compression, spark ignited, internal combustion engines has been practiced for some time.
  • the common organo-metallic compound used for this purpose has been tetraethyl lead (TEL) .
  • TEL tetraethyl lead
  • these organo-metallic compounds have served well as antiknock agents.
  • certain environmental hazards have been associated with the alkyl lead components of these compounds. This circumstance has precipitated a series of Environmental Protection Agency (EPA) mandates which has essentially phased out leaded gasolines.
  • EPA Environmental Protection Agency
  • organomanganese compounds such as cyclomatic manganese tricarbonyls (CMT) , particularly methylcyclopentadienyl manganese tricarbonyl (MMT) , were once accepted alternatives to TEL.
  • CMT cyclomatic manganese tricarbonyls
  • MMT methylcyclopentadienyl manganese tricarbonyl
  • these compounds produced another set of environmental problems. Namely, their use steadily increased the amount of unoxidized and/or partially oxidized hydrocarbon emissions. Fuels containing such organomanganese compounds gradually cause substantially higher levels of hazardous hydrocarbon emissions than are permitted under law.
  • CAA Clean Air Act as amended (42 USC 7445)
  • the CAA under Section 211(f)(4) permits the EPA Administrator to waive the prohibition on new fuel additives in unleaded gasolines ("Waiver") .
  • the CAA specifically bans manganese (“Mn”) additives in unleaded fuels, absent a waiver.
  • Mn manganese
  • the Administrator prior to granting a waiver, the Administrator must determine applicant's waiver request meets the burden of demonstrating that the new fuel or fuel additive will not cause or contribute to the failure of an emission control system or regulated emission standard(s) . Under this section of the CAA, the Administrator has both denied and granted numerous waiver requests.
  • MMT methyl cyclopentadienyl manganese tricarbonyls
  • Applicant's discovery resides in the source of the problem that causes organomanganese compounds to aggravate hydrocarbon emissions over time.
  • Applicant has discovered that the formation of heavy manganese oxides during combustion (e.g. Mn 3 0 4 and Mn 2 0 3 ) are associated with the build up of engine deposits, catalyst plugging, and aggravated hydrocarbon emissions, which are the features responsible for the failure of cyclomatic manganese tricarbonyl compounds to meet CAA regulated emission standards.
  • Applicant has discovered that it is the management of these heavy manganese oxides during combustion that represents the long eluded solution to the problem of organomanganese compounds.
  • Applicant's invention is distinguished from the prior art in that Applicant has discovered the source of the problem together with the means to solve it.
  • Mn 3 0 A and Mn 2 0 3 are the primary and/or only manganese (“Mn") oxidation product formed during combustion.
  • Applicant has discovered that it is the formation of these heavier manganese oxides during [a less than optimum] combustion process that ultimately causes spark plug and catalyst fouling, combustion chamber deposits and the like. This in turn leads to adverse hydrocarbon emission problems, preventing organomanganese compounds from qualifying for ⁇ 211 (f) EPA waivers, and from complying with appropriate environmental standards. Applicant has unexpectedly discovered that by accelerating and improving combustion to an optimum state, thereby controlling and/or eliminating the formation of heavier manganese oxides during combustion, that hazardous combustion emissions (chiefly hydrocarbon emissions) , catalyst plugging, and the like, can be controlled and even reduced. Such control will permit Applicant's fuels to meet required environmental standards and to qualify for ⁇ 211 (f) EPA waivers.
  • Applicant has unexpectedly discovered that the control of these heavier manganese oxides during combustion is primarily a function of 1) increasing combustion burning velocity (flame speed) and 2) reducing combustion temperatures. By increasing the burning velocity (flame speed, fuel economy, etc) , i.e. shortening the interval of combustion, the hazardous emission causing heavier manganese oxides are not readily formed. By increasing burning velocity, when employing an organomanganese compound, combustion is efficient and cleaner. Applicant has unexpectedly discovered that improvements in burning velocity reduces both hazardous HC and NOx emissions.
  • Applicant has also unexpectedly discovered that by reducing combustion temperatures, hazardous combustion emissions can be additionally controlled.
  • the reduction of combustion temperatures helps reduce the formation of problematic heavier manganese oxides during combustion.
  • reductions in combustion temperatures reduces both HC and NOx emissions.
  • compounds/ components and/or means that reduce combustion temperatures are particularly preferred. The greater the temperature reductions, the better.
  • Fuel compositions that as a consequence of their pre- ignition vaporization into the combustion chamber that reduce the vapor fraction's temperature, are also preferred.
  • an integral element of the claimed invention is the engine, itself, which contributes to the beneficial results. This is unexpected because the use of Mn in fuels combusted in such engines in the past has caused an increase in hazardous hydrocarbon and NOx emissions.
  • the practice of this invention includes the utilization of an engine and exhaust system, specially designed for unleaded fuel usage.
  • RVP Pressure
  • compound/components and/or means be they chemical or mechanical, including exhaust oxygen sensing systems, which increase the fuel-air equivalency ratio, resulting in increased burning velocity, are desirable.
  • combustion catalysts that operate to improve combustion, and combustion efficiency, fuel economy, particularity those also reducing combustion temperatures and/ or increasing burning velocities are desirable.
  • Certain molecular features have been identified by Applicant that reduce heavy manganese oxide formation during combustion. They include H, H 2 , CO, and/or 0CH 3 (methoxy radicals) , and/or OH (hydroxyl radicals) . Those compound/components wherein H, H 2 CO, OCH 3 , and/or OH radicals exist, in high relative concentrations and/or become intermediate combustion products are preferred. The higher the relative weight percentage of these structural components in the component/compound and/or that otherwise occur/result during combustion, the better. Such features may be individual or collective. Again, the object is to reduce adverse emissions by increasing burning velocity and/or by reducing combustion temperatures.
  • Those compounds that applicant has thus far identified that are effective in accomplishing this object include: carbon monoxide, ethylene di methyl ether (also known as methylal, di-methoxy methane) , carbonic acid dimethyl ester (also known as dimethyl carbonate) , and methyl tertiary butyl ether (MTBE) , C, to C 6 lower molecular weight alcohols, particularly methanol and ethanol. Applicant believes many others also exist.
  • ethylene di methyl ether also known as methylal, di-methoxy methane
  • carbonic acid dimethyl ester also known as dimethyl carbonate
  • MTBE methyl tertiary butyl ether
  • OCH 3 methoxy radical
  • methanol methylene di methyl ether
  • carbonic acid dimethyl ester dimethyl carbonate
  • Applicant believes these latter compounds to be among the best in accomplishing Applicant's object. Accordingly, those oxygenates which employ methanol and ethanol in their manufacture are likely to be effective and are contemplated within the scope of this invention. It is believed that such a compound's intermediate combustion and other features will positively effect Applicant's object.
  • THF FUEL 0.033025 grams manganese of MMT per liter, 1.6% Tetrahydrofuran by volume, and unleaded gasoline base.
  • the First Test (Test One) measured HC and NOx emissions from the engine over a forty (40) hour, steady state, 1000 rpm, no load cycle. The purpose of this no load, steady state test was to elicit worse case hydrocarbon (HC) emissions over time. This test condition accelerated HC emission degradation from what would have been expected had a much longer durability type test been conducted.
  • Test One The test results for Test One and Test Two are set forth as follows:
  • MEOH FUEL 0.033025 grams Manganese of MMT per liter of composition, 5% methanol and 5% ethanol by volume, and unleaded gasoline base. -Test One-
  • THF FUEL 0.033025 grams Manganese of MMT per liter, 1.6% Tetrahydrofuran by volume, and unleaded gasoline base.
  • This column represents the % change of HC emissions for the last half of Test One.
  • the Manganese, High Mn, and THF fuels all showed materially higher later stage (Column D) HC emissions (3390, 6554, and 4130 ppmc, respectively), than the Base fuel (3067 ppmc) .
  • the ISO/HEX, MEOH, MTBE, METHYLAL, and DMC fuels did not show the high HC emission levels of the Manganese fuel (3390 ppmc) (Column D) .
  • Their HC emission levels instead, were materially lower ranging from 2953 to 2024 ppmc for MEOH and ISO/HEX, respectively (Column D) .
  • the EGT's for all tested fuels are relatively close together.
  • the BASE and Manganese fuels are the same at 707°F (375C)
  • the DMC, MEOH, and METHYLAL fuels range tightly from 717°F (381C) , 722°F (383C) , and 724°F (384C) , respectively.
  • the MEOH, MTBE, METHYLAL, and DMC fuels had lower rates of EGT increase.
  • the MEOH, METHYLAL, and DMC fuels were tightly grouped at 24 ihp.
  • the MEOH fuel was 72°F (22C) lower than the BASE fuel.
  • FIGURE 1 shows that the higher the load, the greater the EGT differences between the two classes of fuels.
  • FIGURE 2 shows that the higher the load, the greater the EGT differences between the two classes of fuels.
  • This Figure shows hydrocarbon emissions of Test Two as a function of engine gas temperatures ("EGT") .
  • EGT engine gas temperatures
  • This Figure shows that there is a direct correlation between HC emissions and engine gas temperatures. The relationship is most notable in the MEOH, MTBE, METHYLAL, and DMC fuels.
  • Figure 2 shows that the HC/EGT rate of change for the various oxygenates is higher than the HC/EGT rate of change for the non-oxygenated fuels.
  • Figure 2 shows that the lower the combustion temperature of a given oxygenate, the lower the HC emissions.
  • FIGURE 3 Combustion Temperatures and NOx Emissions. This
  • Figure shows NOx emission results as a function of EGT.
  • Figure 3 like Figure 2, shows a direct and significant relationship between NOx emissions and EGT for MEOH, MTBE, METHYLAL, and DMC fuels.
  • This Figure clearly shows that at lower EGT's, particularly in the case of the MEOH, MTBE, METHYLAL, and DMC fuels, NOx emissions are much lower than when compared to the BASE and Manganese fuels.
  • FIGURE 4 Indicated Burning Velocity. This Figure measures burning velocity indirectly via fuel economy measurements as a function of load. It is known in the art that increases in fuel economy, absent a BTU boost, is an indicator of a flame speed or burning velocity increase. Figure 4 shows fuel economy in miles per gallon ("mpg") (or 0.42566 kilometers per liter "kpl”) as a function of load (ihp) . Figure 4 shows significant fuel economy (“FE”) differences between the BASE and the oxygenated fuels, beginning almost immediately with the application of load.
  • mpg miles per gallon
  • kpl 0.42566 kilometers per liter
  • FE fuel economy
  • the fuel economy of the Base fuel is 13.2 mpg (5.619 kpl), compared to 15.7 mpg (6.683 kpl), 15.9 mpg (6.768 kpl), 16.5 mpg (7.0234 kpl) and 17.2 mpg (7.321 kpl) for METHYLAL, MEOH, DMC, and MTBE, respectively.
  • These material differences account for a 19% to 30% improvement in fuel economy over the BASE fuel.
  • These FE improvements indicate substantial burning velocity increases for the METHYLAL, MEOH, DMC, and MTBE fuels.
  • Burning Velocity and HC Emissions This Figure shows HC emissions as a function of fuel economy, i.e. indicated burning velocity.
  • Figure 4 shows a strong correlation between increased burning velocity to improvements in HC emissions.
  • Figure 5 clearly shows that increased burning velocity for METHYLAL, MEOH, DMC, and MTBE translates into improved HC emissions. This correlation is most apparent for the MEOH fuel.
  • This Figure shows NOx emissions as a function of fuel economy. This Figure shows a very strong correlation between increased indicated burning velocity to improvements in NOx emissions. This correlation exists for oxygenated fuels, but is not noticeable for the BASE fuel.
  • oxygenated compounds are utilized to accomplish the object of accelerating burning velocity and/or to reduce combustion temperatures, while not required, it is preferred that the oxygen content, as a percent of total weight of the constituent additive compound, be 15% or more of the total weight of the oxygenate. While lower oxygen concentrations are acceptable, the higher the relative oxygen content, as a weight percentage of the total oxygenated compound/component, the more preferred. It is believed that the simpler the compound/component's molecular structure the better. More complicated molecular structure is acceptable, particularly, if the intermediate combustion products enhance burning velocity and/or reduce combustion temperatures.
  • the thermal efficiency (e.g. fuel economy) of the finished fuel containing the component/compound be an improvement over the base fuel alone.
  • Applicant appreciates that numerous means may be employed to achieve the beneficial results contemplated by Applicant's discovery of the source of the problem. Applicant further appreciates that with his discovery of the source of the problem that numerous other components, compounds, oxygenated and non-oxygenated, including combinations thereof, and/or mechanical/chemical means, will be identified by routine investigation to reduce and/or eliminate heavy manganese oxide formation during combustion.
  • problematic, non-Mn containing unleaded fuels absent organomanganese compounds
  • organomanganese compounds may benefit from Applicant's discovery of the source of the problem. It is contemplated that in order to control of hazardous emission from these fuels that organomanganese compounds may be required.
  • Possible C2 to C6 ethers for use in the practice of this invention may include branched and straight chain ethers, di ethers having two oxygen and dual ether linkage, and tri ethers having three oxygens and multiple ether linkages.
  • Non-limiting examples of possible C2 to C6 ethers include dimethyl ether, methyl ethyl ether, di ethyl ether, ethyl propyl ether, methyl normal propyl ether, ethyl isopropyl ether, methyl isopropyl ether, ethyl normal propyl ether, propyl propyl ether, propyl isopropyl ether, isopropyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl tertiary butyl ether, ethyl secondary butyl ether, methyl normal butyl ether, methyl isobut
  • acceptable di ethers include methylene di methyl ether, methylene di ethyl ether, methylene di propyl ether, methylene di butyl ether, and methylene di isopropyl ether.
  • the ether(s) employed should be anhydrous.
  • most C2 - C6 ethers are completely miscible with petroleum hydrocarbons; and it is preferred that such ethers be used in amounts within their solubility limits.
  • an amount of ether in excess of its solubility can be incorporated in the fuel by such means, as for example, use of mutual solvents.
  • ketones that may be acceptable include ketones with three to about twelve carbon atoms.
  • Lower alkenyl ketones are, however, likely to be slightly preferred.
  • Representative lower alkenyl ketones would include diethyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, ethyl butyl ketone, butyl isobutyl ketone, ethyl propyl ketone, and the like.
  • Other 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. It is expected that those ketones where free H, H 2 CO, OCH 3 , and/or OH radicals become intermediate combustion products are likely to be the best candidates. Possible esters that may be acceptable include anisol (methyl ester of benzene) , isopropyl acetate, and ethyl acrylate.
  • the preferred chemical means for achieving these results is by the addition of a compound or combination of compounds and/or components which, individually or in combination, operate to increase flame speeds/burning velocity and/or reduce combustion temperatures.
  • An illustrative example of a desirable fuel composition containing an oxygenated agent would include the oxygenate from about 0.1 to about 20.0 weight percent by oxygen in the composition, with or without co-solvents, and about 0.000264 to about 0.264200 gram manganese per liter of unleaded fuel.
  • a more desirable composition would include the oxygenate from about 0.5 to about 10.0 weight percent by oxygen in the composition, with or without cosolvents, and an organomanganese concentration from about 0.004128 to about 0.099075 grams manganese per liter of the fuel composition. While not required, anhydrous fuel are desirable.
  • Another desirable composition would include the oxygenate from about 1.0 to about 5.0 weight percent by oxygen in the composition, with or without cosolvents, and an organomanganese concentration from about 0.004128 to about 0.066050 grams manganese per liter of the fuel composition.
  • CMT Cyclomatic Manganese Tricarbonyls
  • EOHC engine out hydrocarbon
  • catalyst plugging when constructed to solve Applicant's discovery of the source of the problem, can prevent unacceptable long term hydrocarbon emissions degradation and prevent catalyst plugging.
  • manganese concentrations for example, greater than 1/64, 1/32, or even 1/16 grams of manganese per 3.785 liters are satisfactory. In view of the prior art literature on the subject, this result is quite unexpected. It appears that levels equal to and exceeding 1/8 or even 3/8 gram of manganese per 3.785 liters are quite satisfactory.
  • concentrations of cyclomatic manganese tricarbonyl from about 0.00825 grams to about 0.099075 grams manganese/liter are acceptable; concentrations in the range of about 0.033025 grams to about 0.06605 grams manganese/ liter are preferred.
  • a desirable range is from about 0.000264 to about 0.06605 grams manganese per liter of composition.
  • a more desirable range is from about 0.004128 to about 0.033025 grams manganese per liter of composition.
  • a preferred range is from about 0.004128 to about 0.016512 grams manganese per liter of composition.
  • a preferred cyclomatic manganese tricarbonyl used in the composition is cyclopentadienyl manganese tricarbonyl.
  • a more preferred cyclomatic manganese tricarbonyl is methyl cyclopentadienyl manganese (MMT) .
  • the composition can also contain homologues or other cyclomatic manganese tricarbonyl substitutes. Non- limiting examples of these other acceptable substitutes include the alkenyl, aralkyl, aralkenyl, cycloalkyi, cycloalkenyl, aryl and alkenyl groups.
  • Illustrative and other nonlimiting examples of acceptable cyclomatic manganese tricarbonyl antiknock compounds include benzyleyelopentadienyl 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- naphthy1fluorenyl manganese tricarbonyl; 4.5.6.7- tetrahydroindenyl manganese tricarbonyl; 3-3ethenyl-4, 7- dihydroindenyl manganese tricarbonyl; 2-ethyl 3 (a- phenylethenyl) 4,5,
  • Applicant also contemplates the use of other additives with his ingredients, such as gum and corrosion inhibitors, detergents, multipurpose additives, and scavengers, made necessary or desirable to maintain fuel system cleanliness and control exhaust emissions.
  • Applicant's invention contemplates a method for controlling hazardous combustion emissions originating in internal combustion engines.
  • This method comprises the mixing of a nonleaded gasoline base comprised of hydrocarbons with a cyclopentadienyl manganese tricarbonyl antiknock compound having a manganese concentration from about 0.000264 to about 0.2642 grams of manganese per liter of the fuel composition, together with a chemical and/or mechanical means for reducing the formation of heavy and/or hazardous emission causing oxides of manganese during the combustion of said fuel.
  • Applicants method then contemplates the combustion of said fuel composition in an internal combustion engine; then emitting the resultant engine emissions through an exhaust system, including catalytic exhaust systems; such that the resultant emissions and/or emission control systems meet ⁇ 211 (f) waiver requirements.
  • Applicant's invention also contemplates a method for controlling hazardous combustion emissions originating in internal combustion engines; comprises the mixing of a nonleaded gasoline base comprised of hydrocarbons with a cyclopentadienyl manganese tricarbonyl antiknock compound having a manganese concentration from about 0.000264 to about 0.2642 grams of manganese per liter of the fuel composition, together with a chemical and/or mechanical means for accelerating burning velocity and/or reducing combustion temperatures of said fuel; then combusting said fuel composition in a spark ignited internal combustion engine; then emitting the resultant emissions through an exhaust system, including catalytic exhaust systems; such that the resultant emissions meet ⁇ 211 (f) waiver requirements.
  • Cosolvent(s) may be selected from the group consisting of C2 to C12 aliphatic alcohols, C3 to C12 ketones, C2 to C12 ethers, esters, oxides, phenols, and the like. It is in the scope of this invention to employ one or more co ⁇ solvents within a particular class of cosolvents and/or to employ any one or more classes of cosolvents simultaneously. It is also within the scope of this invention to mix different classes of cosolvents, including mixed alcohols, ethers, esters, oxides, phenols and/or ketones. For example, it has been found that mixed cosolvent alcohols. particularly those in the C2 to C8 range, have a particularly ameliorative effect on both RVP and octane blending values.
  • Acceptable cosolvent concentrations will vary depending upon the other components and their concentrations in the composition, but will normally range from between 0.1 to about 20.0 volume percent of the composition. More desirable concentrations will normally range from between 0.1 and to about 15.0% volume percent of the composition. Preferred concentrations will range from about 0.1 volume percent to 10 volume percent, with the most preferred ranging from about 0.1 to about 5.0 volume percent.
  • the gasoline to which this invention is applied is a lead free gasoline.
  • the gasoline bases in Applicant's fuel composition are conventional motor fuels, boiling in the general range of about 70 degrees to about 440 degrees F. However, boiling ranges outside gasoline ranges are contemplated and may be used. Substantially all grades of unleaded gasoline employed in spark ignition internal combustion engines are contemplated. Other non-internal combustion engine fuel applications are also contemplated.
  • fuel bases may contain both straight runs and cracked stock, with or without alkylated hydrocarbons, reformed hydrocarbons, and the like.
  • Such fuels can be prepared from saturated hydrocarbons, e.g., straight stocks, alkylation products, and the like, with or without detergents, antioxidants, dispersants, metal deactivators, lead scavengers, rust inhibitors, multi-functional additives, emulsifiers, 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 C4 olefins; 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. Dehydrogenation 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.
  • thermally cracked stocks, catalytically cracked stocks and catalytic reformates contain saturated components.
  • Preferred gasoline bases are those having an octane rating of (R + M)/2 ranging from 70-95.
  • a desirable gasoline base should have an olefinic content ranging from 1 to 30 volume percent, 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 70 degrees F to about 115 degrees F and final boiling points ranging from about 380 degrees F to about 437 degrees F as measured by the standard ASTM distillation procedure (ASTM D-86) . Intermediate gasoline fractions boil away at temperatures within these ranges.
  • desirable base gasoline compositions would include as many aromatics with C8 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, isoproplybenzene, 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-butene, 2 methyl-1 butene, 1 pentene, and the like.
  • olefinic content must be closely watched.
  • the least preferred gasoline component in terms of phase stability when using for example alcohols, 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.
  • 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 components, including 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.,
  • the gasoline may further 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 gasoline may contain supplemental valve and valve seal recession protectants. Nonlimiting examples of such additives include boron oxides, bismuth oxides, ceramic bonded CaF2, iron phosphate, tricresylphosphate, phosphorous and sodium based additives, and the like.
  • the fuel may also contain antioxidants, such as 2,6 di-tert-butylephenol, 2,6-di- tert-butyl-p-cresol, and phenylenediamines such as N-N-di- sec-butyl-p-phenylenediamines, N-isopropylphenylene diamine, and the like.
  • antioxidants such as 2,6 di-tert-butylephenol, 2,6-di- tert-butyl-p-cresol, and phenylenediamines such as N-N-di- sec-butyl-p-phenylenediamines, N-isopropylphenylene diamine, and the like.
  • the fuel may contain such additives as F310, polybutene amines, aminated or polymerized detergents, and the like.
  • the gasoline base may contain hydrocarbons boiling outside normal gasoline ranges. It is contemplated in certain occasions these higher boiling point hydrocarbon can be incorporated into a finished normal boiling gasoline by utilizing the azeotroping effect of certain co- solvents/additives. Applicant has found that higher molecular weight C4-C12 alcohols are particularly useful in reducing end boiling point temperatures.

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Abstract

Compositions de carburant sans plomb constituées par un composé de tricarbonyle de manganèse cyclomatique (CMT), de préférence de tricarbonyle de manganèse de méthylcyclopentadiényle (MMT) et moyens permettant de limiter la formation d'oxydes de manganèse lourds pendant la combustion, de façon à rendre les émissions d'échappement acceptables pour l'environnement.
EP93920308A 1992-08-24 1993-08-24 Composition de carburant sans plomb a base de mmt Pending EP0656045A1 (fr)

Applications Claiming Priority (3)

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US93419292A 1992-08-24 1992-08-24
US934192 1992-08-24
PCT/US1993/007962 WO1994004636A1 (fr) 1992-08-24 1993-08-24 Composition de carburant sans plomb a base de mmt

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JP (2) JP3478825B2 (fr)
KR (1) KR100307417B1 (fr)
AU (1) AU5089593A (fr)
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WO (1) WO1994004636A1 (fr)

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EP0748364B1 (fr) * 1994-03-02 2007-11-21 ORR, William C. Compositions de carburant sans plomb
EP0763079A1 (fr) * 1994-05-31 1997-03-19 ORR, William C. Procedes et compositions pour combustion en phase vapeur
BR9608589A (pt) * 1995-06-07 1999-09-14 Willian C Orr Composições e processo de combustão em fase vapor
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
US6206940B1 (en) * 1999-02-12 2001-03-27 Exxon Research And Engineering Company Fuel formulations to extend the lean limit (law770)
BRPI0809980B1 (pt) * 2007-04-04 2017-02-14 Lubrizol Corp composição de combustível e método de alimentação de combustível em um motor de combustão interna
KR100881756B1 (ko) 2007-10-15 2009-02-06 주식회사 성우지오텍 펜턴반응의 고도산화공법을 이용한 배기가스 정화방법 및 정화장치
US8741002B2 (en) 2009-05-25 2014-06-03 Shell Oil Company Gasoline compositions
EP2435542B1 (fr) 2009-05-25 2019-02-27 Shell International Research Maatschappij B.V. Compositions d'essence

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US4141693A (en) * 1974-12-18 1979-02-27 Standard Oil Company (Ohio) Manganese containing fuels
US4005993A (en) * 1976-03-08 1977-02-01 Ethyl Corporation Novel gasoline compositions
ATE69462T1 (de) * 1985-08-28 1991-11-15 William C Orr Bleifreie brennstoffzusammensetzung.
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JP2004003500A (ja) 2004-01-08
KR100307417B1 (ko) 2001-11-30
JP4054288B2 (ja) 2008-02-27
WO1994004636A1 (fr) 1994-03-03
CA2142991A1 (fr) 1994-03-03
JPH08500624A (ja) 1996-01-23
KR950703044A (ko) 1995-08-23
AU5089593A (en) 1994-03-15

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