US2938777A - Gasoline fuel composition - Google Patents

Gasoline fuel composition Download PDF

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Publication number
US2938777A
US2938777A US718108A US71810858A US2938777A US 2938777 A US2938777 A US 2938777A US 718108 A US718108 A US 718108A US 71810858 A US71810858 A US 71810858A US 2938777 A US2938777 A US 2938777A
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Prior art keywords
gasoline
engine
deposits
fuel
additive
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US718108A
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Jr Thomas F Banigan
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Tidewater Oil Co
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Tidewater Oil Co
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Priority claimed from US579171A external-priority patent/US2853530A/en
Application filed by Tidewater Oil Co filed Critical Tidewater Oil Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/198Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters

Definitions

  • This invention relates to a fuel for internal combustion engines containing an additive, whereby cleaner operation is obtained.
  • Thisapplication is a division of Serial No. 579,171 filed April 19, 1956, wherein the gasoline additive itself and the method for its preparation are claimed. Said application issued September 23, 1958 as Patent Number 2,853,530.
  • One object of the invention is to provide a cleaner fuel for internal combustion engines, such as automobile engines.
  • Progress in the automobile industry has resulted in the development of gasoline engines of increasingly higher compression pressures, requiring gasoline fuels with correspondingly higher anti-knock properties or octane rating.
  • Modern refiners in an effort to obtain adequate yields of high octane gasoline are resorting to the newer processes of catalytic cracking, catalytic reforming and polymerization, and delayed or fluid coking.
  • the stocks from such processes can provide the desired octane rating, but unfortunately such stocks often contain unstable components which tend to form deposits in critical parts of the induction system such as the carburetor throat, intake manifold and intake valve ports.
  • the polyether has approximately the following physical properties: g Q g Y Boiling point, ".C.: f
  • An important object of this invention is, therefore, to provide a fuel that has substantially less tendency to buildup intake manifold and engine deposits.
  • Another object of the' invention isto obtain cleaner carburetion by providing a fuel that does not foul up the carburetor.
  • Another object of the invention is to prevent loss of power by reducing the tendency for piston-ring sticking.
  • the polyether is a colorless, slightly viscous liquid. It is completely miscible with organic solvents 'such as benzene, Xylene, pentane, octane, iso-octane, ethyl alcohol
  • organic solvents ' such as benzene, Xylene, pentane, octane, iso-octane, ethyl alcohol
  • the compound is stable, as'shown by the fact that one sample stored for .eight months, in a clear bottle, showed no.
  • the compound is in-i flammable, burning readily with no smoke and essentially and ethyl ether, but only partially soluble in water.
  • the test procedure involves a 40 hour engine run on a dynamometer under conditions chosen to correlate, on an accelerated scale, with field performance.
  • a 216.5 cubic-inch, six-cylinder Chevrolet engine is run continuously for forty hours at a speed of 1900 r.p.m. (plus or minus 25 r.p.m.) under an engine load of 36 B.H.P. (plus or minus 1 B.H.P.).
  • the jacket coolant inlet temperature is kept at F. minimum, the jacket coolant outlet temperature is kept Within two degrees of F., and the crankcase oil temperature is kept within two degrees of F.
  • the air-fuel ratio is 14.5 (plus or minus 0.5) to 1.
  • the spark advance is 35 (plus or minus 3).
  • the spark plug gap, ignition cam angle, valve clearance, exhaust back pressure and other similar conditions are also maintained at predetermined values.
  • a perfectly clean engine will thus rate 100.
  • a total rating of 85 is considered acceptable if the piston skirtvarnishis 7.5 or better.
  • the gasoline employed in the tests discussed hereinafter for illustration was composed of about 50% mixed thermal naphtha having about 95 400 F. boiling range, about 20% light straight-run naphtha having 95-250 F. boiling range, about 25% heavy cracked (catalytic) naphtha having 270-400 F. boiling range, and about of light natural gasoline. It contained as additives about 1.75 ml. per gallon of tetraethyllead and an amine inhibitor in normal amounts. It analyzed 0.11% sulfur. Gum was present at about 2 to 5 mg. per 100 ml. in the ASTM test and the copper dish test showed about 16-26 mg. of gum per 100 ml. The gasoline had the following volatility. specifications: evaporated at 134150 F., 50% at 244-250 F., and'90% at about 360 F. The approximate composition of the gasoline was:
  • Table I shows the results of such tests where 0.75 cc./ gal. of the new compound of this invention was used, in comparison with the same gasoline without the bis [2-(1-methoxyisopropoxyisopropoxy) ethyl] ether.
  • the new compound contained about 2% by weight of an antioxidant (phenylalphanaphthylamine) which had been added to assure against possible oxidation in storage and blending operations.
  • an antioxidant phenylalphanaphthylamine
  • Table H shows a breakdown of some of the items in the same test as Table I.
  • a fuel according to claim 1 wherein the concentration of the additive is about 0.75 cc. per gallon of gaso line.

Description

United States Patent O GASOLINE FUEL COMPOSITION Thomas F. Banigan, Jr., Walnut Creek, Ca1if., assignor to Tidewater Oil Company, a corporation of Delaware No Drawing. Original application Apr. 19, 1956, Ser. No. 579,171, now Patent No. 2,853,530, dated Sept. 23, 1958. Divided and this application Feb. 19, 1958, Ser. No. 718,108
2 Claims. (CI. 44-77) This invention relates to a fuel for internal combustion engines containing an additive, whereby cleaner operation is obtained. Thisapplication is a division of Serial No. 579,171 filed April 19, 1956, wherein the gasoline additive itself and the method for its preparation are claimed. Said application issued September 23, 1958 as Patent Number 2,853,530.
One object of the invention is to provide a cleaner fuel for internal combustion engines, such as automobile engines. Progress in the automobile industry has resulted in the development of gasoline engines of increasingly higher compression pressures, requiring gasoline fuels with correspondingly higher anti-knock properties or octane rating. Modern refiners in an effort to obtain adequate yields of high octane gasoline are resorting to the newer processes of catalytic cracking, catalytic reforming and polymerization, and delayed or fluid coking. The stocks from such processes can provide the desired octane rating, but unfortunately such stocks often contain unstable components which tend to form deposits in critical parts of the induction system such as the carburetor throat, intake manifold and intake valve ports. Heretofore, use of gasolines made from these stocks has commonly resulted in fouling such parts in a few thousand miles, especially where the cars have been subjected to city driving or otherlow-output types of use. As these depositsaccumulate, the 'engines idling becomes labored and uneven, and stalling often results. Deposits also form in the combustion chamber, and,'as a result of the various deposits, the engine exhibits a loss of power, gives poor gasoline mileage, and. eventu ally requires higher octane fuel.
These conditions are the result of unstable constituents in the fuel reacting under the influence of heat, oxygen, blowby gases and exhaust gases. While it might be possible to refine all unstable constituents out of the fuel, it is generally not feasible to do so. The depositforming tendency at times is accentuated when lead tetraethyl and dyes are present.
Many substances have been tried as gasoline additives in attempts to solve the above problems, but the results have fallen far short of expectations. Various detergents and gum solvents have been mixed with the gasoline in an attempt to prevent the formation of deposits. Many volatile polar compounds which should be capable of dissolving the deposits have been tried, unsuccessfully. Acetone and other ketones, tetrahydrofuran, oxydipropionitrile, iminodipropionitrile, morpholine, quinoline, cyclohexanone, nitrobenzene, di-tertiarybutyl-paracresol, polypropylene'glycols and ammonium mahogany sulfonate are among the compounds tried. None of these appear to give improvement in overall engine cleanliness; some of them decrease deposits in one part of the engine only to transfer what they pick up to other parts of the engine, where they are redeposited. Some of these contribute to the deposits in the carburetor and on the valve stems; some cause ring sticking; and some increase overall dirtiness throughout the engine.
- appear from-the following description.
The polyether has approximately the following physical properties: g Q g Y Boiling point, ".C.: f
at 770 mm. (atmos. press.) 185 Refractive index, n 1.4214 Density, df 0.95.27
Molecular refraction? V Experimental (Lorentz & Lorenz) 97.5
' "Theoretical (Auwers' &' Eisenlohr) J.. 1 96:8" Viscosity:
Saybolt seconds 100 F. 34.3 Centistokes 100 F. 2.46 Carbon residue, less than 0.01 Solubility in water 25C., g./ 100g. 12
2,938,777. Patented May 31,
Other types of gasoline additives, such as tricresyl phosphate, do not reduce the engine deposits but rely instead on chemical change of the deposits in the combustion chamber to suppress preignition usually resulting from such deposits. Thistype of additive is of no value in preventing induction system deposits or piston-ring sticking. H
An important object of this invention is, therefore, to provide a fuel that has substantially less tendency to buildup intake manifold and engine deposits.
Another object of the' invention isto obtain cleaner carburetion by providing a fuel that does not foul up the carburetor. v I
Another object of the invention is to prevent loss of power by reducing the tendency for piston-ring sticking.
Other objects and advantages of the invention will Bis [2-( 1-methoxyisopropoxyisopropoxy) has the formula CH -(OC H -CH -O-(CH -O- OC H -CH -0 CH This substance is. claimed in application'SerialNo.579,171 filed April 19, 1956', and its preparation is therein described and claimed.
Said application issued September 23,1958 as Patent Number 2,853,530.
The polyether is a colorless, slightly viscous liquid. It is completely miscible with organic solvents 'such as benzene, Xylene, pentane, octane, iso-octane, ethyl alcohol The compound is stable, as'shown by the fact that one sample stored for .eight months, in a clear bottle, showed no. The compound is in-i flammable, burning readily with no smoke and essentially and ethyl ether, but only partially soluble in water.
change in color or properties.
no carbon residue.
Performance tests have shown that the present invention produces substantial improvement in engine. cleanliness, as compared to the same fuel not containing the additive. The test procedure (designated hereinafter as 40-E procedure) involves a 40 hour engine run on a dynamometer under conditions chosen to correlate, on an accelerated scale, with field performance. In this test a 216.5 cubic-inch, six-cylinder Chevrolet engine is run continuously for forty hours at a speed of 1900 r.p.m. (plus or minus 25 r.p.m.) under an engine load of 36 B.H.P. (plus or minus 1 B.H.P.). The jacket coolant inlet temperature is kept at F. minimum, the jacket coolant outlet temperature is kept Within two degrees of F., and the crankcase oil temperature is kept within two degrees of F. The air-fuel ratio is 14.5 (plus or minus 0.5) to 1. The spark advance is 35 (plus or minus 3). The spark plug gap, ignition cam angle, valve clearance, exhaust back pressure and other similar conditions are also maintained at predetermined values. Before the test, the engine is disassembled and cleaned, and a new set of piston rings is installed. The
ethyl] ether On these first seven items, the rating runs between for dirty to 10 for clean.. v i i (8) Corrosion or rust rating (IO for none, 9 for light, 8 for medium, and 7 for heavy corrosion).
. (9) Stuck ring rating (10, minus 0.5 demerit for each 90of n'ng stuck in the groove).
(10) Tight ring rating (10, minus 0.5 demerit for each tight ring).
A perfectly clean engine will thus rate 100. A total rating of 85 is considered acceptable if the piston skirtvarnishis 7.5 or better.
The gasoline employed in the tests discussed hereinafter for illustration was composed of about 50% mixed thermal naphtha having about 95 400 F. boiling range, about 20% light straight-run naphtha having 95-250 F. boiling range, about 25% heavy cracked (catalytic) naphtha having 270-400 F. boiling range, and about of light natural gasoline. It contained as additives about 1.75 ml. per gallon of tetraethyllead and an amine inhibitor in normal amounts. It analyzed 0.11% sulfur. Gum was present at about 2 to 5 mg. per 100 ml. in the ASTM test and the copper dish test showed about 16-26 mg. of gum per 100 ml. The gasoline had the following volatility. specifications: evaporated at 134150 F., 50% at 244-250 F., and'90% at about 360 F. The approximate composition of the gasoline was:
Y p H V I Percent Paraflins and naphthalenes "about 66 Olefins ut 16 Aromatics out 18 Sulfur out 0.1 Phenols out 0.4 Nitrogen ut 0.001
Table I shows the results of such tests where 0.75 cc./ gal. of the new compound of this invention was used, in comparison with the same gasoline without the bis [2-(1-methoxyisopropoxyisopropoxy) ethyl] ether.
As blended into the gasoline, @the new compound contained about 2% by weight of an antioxidant (phenylalphanaphthylamine) which had been added to assure against possible oxidation in storage and blending operations.
' Table I Gasoline Plus Additive gm./ gal.
Control Gasoline Overall Rating"... -L.' 83
Table H shows a breakdown of some of the items in the same test as Table I.
The superior stuck-ring-rating of the gasoline containing the new additive is particularly impressive.
I' claim:
1. A gasoline containing bis[2-(l-methoityisopropoxyisopropoxy) ethyl] ether as an additive in amount sulficient to substantially reduce engine deposits.
2. A fuel according to claim 1 wherein the concentration of the additive is about 0.75 cc. per gallon of gaso line. e
' References Cited in the file of this patent UNITED STATES PATENTS Toussaint et 'al. Aug. 19, 1947 2,425,845 2,563,101 Colwell et a1. Aug. 7, 1951 2,800,400 Hughes July 23, 1957 2,807,526
Foreman Sept. 24, 1957

Claims (1)

1. A GASOLINE CONTAINING BIS(2-(1-METHOXYISOPROPOSYISOPROPOXY) ETHYL) ETHER AS AN ADDITIVE IN AMOUNT SUFFICIENT TO SUBSTANTIALLY REDUCE ENGINE DEPOSITS.
US718108A 1956-04-19 1958-02-19 Gasoline fuel composition Expired - Lifetime US2938777A (en)

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US579171A US2853530A (en) 1956-04-19 1956-04-19 Bis [2-(1-methoxysopropoxyisopropoxy) ethyl] ether
US718108A US2938777A (en) 1956-04-19 1958-02-19 Gasoline fuel composition

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0282845A1 (en) * 1987-03-14 1988-09-21 BASF Aktiengesellschaft Fuels containing small amounts of alkoxylate and polycarboxylic acid imide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425845A (en) * 1945-04-21 1947-08-19 Carbide & Carbon Chem Corp Mixtures of polyoxyalkylene diols and methods of making such mixtures
US2563101A (en) * 1948-03-08 1951-08-07 Thompson Prod Inc Fuel charge for internalcombustion engines
US2800400A (en) * 1953-12-24 1957-07-23 Standard Oil Co Motor fuel additive and fuel containing same
US2807526A (en) * 1950-10-04 1957-09-24 Standard Oil Co Additive for motor fuels and fuel compositions containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425845A (en) * 1945-04-21 1947-08-19 Carbide & Carbon Chem Corp Mixtures of polyoxyalkylene diols and methods of making such mixtures
US2563101A (en) * 1948-03-08 1951-08-07 Thompson Prod Inc Fuel charge for internalcombustion engines
US2807526A (en) * 1950-10-04 1957-09-24 Standard Oil Co Additive for motor fuels and fuel compositions containing the same
US2800400A (en) * 1953-12-24 1957-07-23 Standard Oil Co Motor fuel additive and fuel containing same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0282845A1 (en) * 1987-03-14 1988-09-21 BASF Aktiengesellschaft Fuels containing small amounts of alkoxylate and polycarboxylic acid imide

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