Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates

Definitions

• This invention concerns an improved motor fuel composition and an improved method of operating an internal combustion engine. More particularly, the invention concerns incorporating into a motor fuel, such as gasoline, an additive or combination of additives that will improve the geometric and time distribution of the fuel in the induction system of an aspirated multicylinder internal combustion engine.
• a motor fuel such as gasoline
• an additive or combination of additives that will improve the geometric and time distribution of the fuel in the induction system of an aspirated multicylinder internal combustion engine.
• Gasolines used as motor fuels comprise a mixture of hydrocarbons of various boiling points.
• a gasoline can have an initial boiling point in the range of about 70 to 135 F. and a final boiling point in the range of about 250 to 450 F.
• the mixture of gasoline and air that leaves the carburetor and passes to the various cylinders through the intake manifold tends to deposit some of the higher boiling fractions in the form of a liquid film on the walls of the intake manifold. This liquid film is the main factor in poor fuel distribution in the engine. Accordingly, it is desirable for improved efficiency to have the gasoline as a vapor or spray in the air-fuel mixture.
• the distribution of the air-fuel mixture to the various cylinders of an aspirated multicylinder internal combustion engine can be improved by incorporating in the fuel fed to that engine a minor amount of one or more aliphatic amines having a long straight chain of from 12 ice to 20 carbon atoms, preferably 16 to 18 carbon atoms.
• One such amine that is used will be a tertiary amine having one such long straight aliphatic chain and two short alkyl chains of no more than three carbon atoms, i.e. an amine of the formula:
• R is a straight chain aliphatic hydrocarbon radical of from 12 to 20 carbon atoms, preferably C to C and R and R" are C, to C alkyl, e.g. propyl or isopropyl, methyl, or ethyl, preferably C to C and most preferably methyl.
• a mixtuer of a tertiary amine as above described with a primary amine i.e. one wherein in the above formula R is a straight chain aliphatic group of 12 to 20 carbon atoms, preferably C to C and R and R" are hydrogen.
• straight chain hydrocarbyl amines of this invention can be either saturated or unsaturated aliphatic tertiary amines or mixed tertiary and primary amines, the saturated amines are preferred.
• Representative straight chain aliphatic primary amines useful in this invention include normal octadecyl amine, normal octadecenyl amine, normal dodecyl amine and normal hexadecyl amine.
• a particularly useful commercial mixture of primary amines is hydrogenated tallow amine wherein the aliphatic groups are principally C and C
• Tertiary amines used in this invention include, for example, dimethyl octadecyl amine, diethyl dodecyl amine, methyl ethyl .tetradecyl amine, and diisopropyl hexadecyl amine.
• a particularly useful commercial mixture of tertiary amines is dimethyl hydrogenated tallow amine, wherein the long straight chain hydrocarbon groups of the tallow moiety are principally C and C
• other amino compounds have been proposed for addition to gasoline.
• U.S. Pat. 3,399,982 discloses tertiary alkyl primary amines such as 2- methyl-Z-aminohexadecane and 2-methyl-2-aminooctaeicosane. Amines of this type that were subjected to testing gave little or no improvement in air/fuel ratio distribution and hence were not considered to be useful in the present invention.
• -It is also known to incorporate various aromatic amines and cycloaliphatic amines into gasoline to be used as antioxidants.
• Such amines include phenyl alpha-naphthylamine, cyclohexylamine, n-butyl-p-aminophenol, xylidine and alkylated p-phenylene diamines.
• Amino compounds of this type do not have the proper surface activity to make them useful in the present invention.
• Straight chain aliphatic amines have been suggested as anti-icing agents for gasolines when added in concentrations of about 0.2 to 0.5 percent by volume (see US. Pat. 2,706,677). Such concentrations of the amines are much greater than the concentrations used in the present invention.
• the amines added to gasoline in accordance with the present invention act in some way on the walls of the intake manifold of the gasoline engine to render them less subject to wetting by the gasoline and thereby reduce the tendency for deposition of the liquid film referred to above and increase the proportion entrained in the air. This reduces the variation from cylinder to cylinder in the air/ fuel ratio of the mixreduced. In general, the result is improved smoothnessof operaton, reduced tendency for hesitation on acceleration, reduced tendency for surging at constant road speeds, and improved gasoline mileage. There is also generally a reduction in the emission of carbon monoxide and unburned hydrocarbons, thereby reducing air pollution.
• the aliphatic amines of this invention will be used in gasoline in a total concentration within the range of from about to about 80 pounds per thousand barrels of gasoline, a barrel containing 42 U.S. gallons.
• the preferred concentration range is from about to about 40 pounds per thousand barrels.
• a concentration range of from 10 to 40 pounds per thousand barrels is roughly equal to a weight percent concentration of from about 0.004 to about 0.016 weight percent.
• the tertiary amines can be employed using only one or more of the tertiary amines, it is preferred to employ a mixture of primary and tertiary amines of the types described.
• the proportions of amines can range from about 75 percent primary and 25 percent tertiary up to substantially all tertiary and no primary amine.
• the amonut of tertiary amine will be at least equal the amount of primary amine in the mixture.
• a particularly useful combination comprises three parts of tertiary for each part of primary amine.
• the tertiary amines of this invention improve the solubility of long straight chain aliphatic primary amines, especially hydrogenated tallow amine. This is a decided advantage, since the preferred primary amines have limited solubility in all suitable solvents, particularly at low temperatures. This is especially helpful when preparing an additive concentrate for later blending into gasoline.
• a blend of 5 weight percent of hydrogenated tallow amine, weight percent of dimethyl hydrogenated tallow amine and 80 weight percent of a mixture of 3 volumes of xylene and 1 volume of isopropanol has more solubility stability than a blend of 5 weight per cent of hydrogenated tallow amine and 95 weight percent of the 3 to 1 mixture of xylene and isopropanol, particularly at low temperatures.
• an additive concentrate can be prepared containing from 5 to 10 weight percent of primary amine or mixed primary amines and from 10 to 30 percent of tertiary amine or mixed tertiary amines along with a solvent for the amines.
• the preferred solvent in the concentrate comprises a mixture of an aromatic hydrocarbon and a polar solvent, most usually about 1 to 4 volumes of aromatic hydrocarbon being used per volume of polar solvent.
• the aromatic solvents include ortho or meta xylene, mixed xylenes, toluene, ethylbenzne, etc.
• the polar solvents include C to C aliphatic alcohols, glycols of 6 to 8 carbon atoms such as 2-methyl-2,4-pentane diol (known as hexylene glycol), 2-methyl-1,3-pentane diol, 2-ethyl- 1,3-hexane di-ol, etc., and glycol ethers of from 3 to 8 carbon atoms including, Z-methoxyethanol (methyl Cellosolve), 2-butoxy ethanol (butyl Cellosolve), 3-ethoxy propanol, etc.
• Preferably 1 to 2 volumes of the polar solvent are used for each 3 volumes of aromatic hydrocarbon solvent.
• the additive concentrate can also contain other additives that are commonly blended into gasoline, e.g. antioxidants, dispersants, rust inhibitors, etc.
• the gasolines in which the additives of this invention are employed are conventional petroleum distillate fuels boiling in the gasoline range and intended for internal combustion engines, preferably spark ignition engines.
• Gasoline is defined as a mixture of liquid hydrocarbons having an initial boiling point in the range of about 70 to F. and a final boiling point in the range of about 250 to 450 F. Gasolines are supplied in a number of different grades, depending upon the type of service for which they are intended.
• the additives of the invention are particularly useful in motor and aviation gasolines.
• Mot-or gasolines include those defined by ASTM Specification D-439-58T, Types A, B and C.
• gasolines are composed of a mixture of various types of hydrocarbons, including aromatics, olefins, paraffins, isoparaflins, naphthenes, and' occasionally, diolefins. Not all of these types of hydrocarbons will necessarily be present in a particular gasoline.
• These fuels are derived from petroleum crude oil by refining processes such as fractional distillation, catalytic cracking, hydroforming, alkylation, isomerization, polymerization and solvent extraction, etc.
• Motor gasolines normally have boiling ranges between about 70 F. and about 450 F., while aviation gasolines have narrower boiling ranges of between 100 F. and 330 F.
• the vapor pressures of gasoline as determined by ASTM Method D-323 vary between about 5 and about 18 p.s.i. at 100 F.
• the properties of aviation gasolines are set forth in US. Military Specification MIL-F-5572 and ASTM Specification D-9 1 0-5 7T.
• the additives employed in accordance with this invention may be used in gasolines with other additive agents conventionally used in such fuels.
• alkyl lead anti-knock agents such as tetraethyl lead, tetramethyl lead, dimethyl diethyl lead, or a similar alkyl lead antiknock agent or olefinic lead antiknock agent such as tetravinyl lead, triethyl vinyl lead, and the like, or a combination thereof
• alkyl lead anti-knock agents such as tetraethyl lead, tetramethyl lead, dimethyl diethyl lead, or a similar alkyl lead antiknock agent or olefinic lead antiknock agent such as tetravinyl lead, triethyl vinyl lead, and the like, or a combination thereof
• motor gasolines and in aviation gasolines along with the usual scavenging agents such as ethylene dichloride or ethylene dibromide.
• scavenging agents such as ethylene dich
• i antioxidants i antioxidants, antistatic agents, solvent oils, lead octane appreciat-ors, e.g., t-butyl acetate, auxiliary scavengers like tri- [i-chloroethyl phosphate, dyes, anti-icing agents, e.g. isopropanol, hexylene glycol, and the like.
• auxiliary scavengers like tri- [i-chloroethyl phosphate, dyes, anti-icing agents, e.g. isopropanol, hexylene glycol, and the like.
• oil-soluble dispersants and detergents to provide significant improvement in overall engine cleanliness. This is taught, for example, by Calvino et al. in US. Pat. 3,223,495.
• EXAMPLE 1 (INCLUDING COMPARATIVE TESTS) Gasoline blends were prepared using as the base a 100 octane rating gasoline that had the inspections shown in Table I:
• the blends were prepared by adding, by simple mixing, normal octadecyl amine at the concentration of 40 pounds per thousand barrels to one portion of the base fuel, and dimethyl normal hexadecyl amine to another portion of the base fuel at the same concentration.
• the base fuel and each blend were run separately in a 1967, 6-cylinder, 175 cu. inch Valiant engine equipped with exhaust emission controls meeting the requirements of the State of California for 1967.
• the Valiant car was operated on a Clayton dynamometer with acceleration weights equivalent to 4,000 pounds.
• the engine was run at idle speed and at 50 miles an hour and the air/fuel ratio reaching each cylinder was determined.
• sampling lines were extended into the individual exhaust valve ports of the engine, so as to permit the analysis of the combustion products from each of the six cylinders separately.
• the exhaust gas was filtered and cooled prior to analysis to remove solid particles and most of the water produced by combustion of the gasoline.
• the exhaust gas was then analyzed for hydrocarbons, carbon monoxide, carbon dioxide, nitrogen oxide and oxygen.
• Air/fuel ratios were calculated by a material balance of the exhaust gas, using well-known procedures (see Lamont 'Eltinge, Fuel/Air Ratio and Distribution From Exhaust Gas Compositions, SAE Paper 680114, January 1968; and R. S. Spindt, Air/Fuel Ratios From Exhaust Gas Analysis, SAE Paper 650507, May 1965).
• the spread between the highest and lowest calculated air/fuel ratio at each of the testing speeds for each of the fuels is given in the follwoing Table II.
• the air/ fuel ratios were in the range of 13/1 to 15/1 at idle and in the range of 14.5/1 to 16.5/1 at 50 miles per hour.
• Dicoco 12 Tallo 27 20 Dimethyl n-hexadecyl 36 27 Dimethyl n-oetadeeyl 18 15 Hydrogenated tallow 30 25
• Dicoco amine is a mixture of secondary amines derived from coconut oil. The major component is a secondary amine having two aliphatic groups of 12 carbon atoms each. Tallow amine is a mixture of saturated and unsaturated primary aliphatic amines, predominantly C and C amines. Hydrogenation of tallow amine removes substantially all the unsaturation.
• EXAMPLE 3 (FUEL ECONOMY TESTS) The effect of tallow amine and of a mixture of hydrogenated tallow amine and dimethyl n-octadecyl amine upon fuel economy was determined in the following manner. Standard commercial automobiles were used and each was run through the same preselected driving sequence on a mileage accumulation dynamometer. The latter is described in US. Pat. 3,050,994. Each car was first run with the base fuel described in Table I for a period of 64 hours and the fuel economy was determined. Each car was then run through the same sequence for the same period of time using the base fuel of Table I to which had been added tallow amine at a concentration level of 40 pounds per thousand barrels and the fuel economy was again observed.
• EXAMPLE 4 (ADDITIVE CONOENTRATE)
• EXAMPLE 5 (ADDITIVE CONCENTRATE)
• a crystallization inhibitor about 0.5 part of a 50 weight percent concentrate, in mineral lubricating oil, of a condensate of chlorinated paraflin wax and naphthalene, e.g. the commercial product known as Parafiow 149.
• EXAMPLE 6 As stated earlier, variations in air/fuel ratio in particular cylinders of a multicylinder engine can vary with respect to time. Such variations cause an engine to accelerate as frequently as once per second, even though an attempt is made to hold the vehicle under steady cruise conditions with a fixed position of the throttle. If the variation in air/fuel ratio with time becomes sufiiciently severe, it feels to the automobile driver as if his car is being buffeted by winds. The present invention reduces this phenomenon and gives a significant improvement in steadiness at fixed cruise conditions, as is demonstrated by the following tests. A 1969 Pontiac automobile having a 400 cubic inch displacement engine and an automatic transmission was driven in two opposite directions over a stretch of highway at 50 miles per hour. An electronic tachometer measured the engine r.p.m.
• the car was first operated with the 100 octane base fuel described in Table I. The car was then operated over the same stretch of highway with the same base fuel into which had been blended hydrogenated tallow amine at the rate of 10 pounds per thousand barrels of gasoline plus dimethyl n-octadecyl amine at the rate of 30 pounds per thousand barrels.
• a gasoline composition comprising a major proportion of gasoline into which has been incorporated from about to about 80 pounds, per thousand barrels of gasoline, of a mixture of aliphatic amines, one of said amines being an aliphatic primary amine having a long straight chain of from 12 to 20 carbon atoms, the second amine being an aliphatic tertiary amine having one long straight chain of from 12 to 20 carbon atoms and two short chain alkyl groups of from 1 to 3 carbon atoms.
• composition as defined by claim 1 wherein the quantity of said tertiary amine is from about 1 to 5 times the quantity of said primary amine.
• composition as defined by claim 1 wherein the amine concentration is from 10 to 40 pounds per thousand barrels of gasoline.
• composition as defined by claim 1' wherein the long straight chain in each of said amines is predominantly 16 to 18 carbon atoms in length.
• composition as defined by claim 1 wherein said primary amine is hydrogenated tallow amine.
• composition as defined by claim 1 wherein said tertiary amine is dimethyl hydrogenated tallow amine.
• a gasoline composition comprising a major proportion of gasoline into which has been incorporated from about 5 to about pounds per thousand barrels of gasoline, of an aliphatic tertiary amine having one long straight chain of from 12 to 20 carbon atoms and two short chain alkyl groups of from 1 to 3 carbon atoms.
• composition as defined by claim 9 wherein said amine is predominantly dimethyl n-octadecyl amine.
• An additive concentrate for a gasoline composition which comprises from about 5 to 10 weight percent of an aliphatic primary amine having a straight chain aliphatic group of from 12 to 20 carbon atoms, from about 10 to 30 weight percent of an aliphatic tertiary amine having one long straight chain of from 12 to 20 carbon atoms and two alkyl groups of from 1 to 3 carbon atoms, and from 60 to weight percent of a solvent, said solvent comprising a mixture of a liquid aromatic hydrocarbon and a polar solvent.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1970
  • 1970-03-16 US US20083A patent/US3707362A/en not_active Expired - Lifetime
• 1971
  • 1971-03-12 JP JP1315571A patent/JPS542207B1/ja active Pending
  • 1971-03-12 NO NO00940/71A patent/NO129958B/no unknown
  • 1971-03-15 SE SE7103302A patent/SE373380B/xx unknown
  • 1971-03-15 DE DE2112321A patent/DE2112321C2/de not_active Expired
  • 1971-03-15 BE BE764246A patent/BE764246A/xx not_active IP Right Cessation
  • 1971-03-15 FR FR7108898A patent/FR2084614A5/fr not_active Expired
  • 1971-03-16 NL NLAANVRAGE7103496,A patent/NL168873C/xx not_active IP Right Cessation
  • 1971-03-16 DK DK125571AA patent/DK126790B/da unknown
  • 1971-04-19 GB GB2319871*A patent/GB1339066A/en not_active Expired

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