US3425815A - Synergistic additive mixture - Google Patents

Synergistic additive mixture Download PDF

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Publication number
US3425815A
US3425815A US454167A US3425815DA US3425815A US 3425815 A US3425815 A US 3425815A US 454167 A US454167 A US 454167A US 3425815D A US3425815D A US 3425815DA US 3425815 A US3425815 A US 3425815A
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acid
alkyl
mixture
salts
monoand
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Robert H Rosenwald
Russell F Stedman
James C Hughes
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Universal Oil Products Co
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Universal Oil Products Co
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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts

Definitions

  • the novel additive mixture is used in fuels supplied to carbureted internal combustion engines.
  • a serious problem in the operation of automobiles is stalling of the engine due to the formation of ice in the carburetor throttle body and on the throttle plate.
  • the periods of relatively high humidities, such stalling has been encountered under idling or low load conditions. This is caused by the air-borne moisture undergoing freezing due to the refrigerating effect encountered in normal fuel vaporization Within the carburetor.
  • the ice formed on the throttle plate and adjacent carburetor walls restricts the narrow air Openings and causes engine stalling.
  • the icing problem is of increasing importance because of the design of newer automobiles. For example,
  • the present invention relates to a method of preventing stalling due to icing and of main taining carburetor cleanliness of a carbureted combustion engine which comprises supplying to said engine a hydrocarbon fuel containing a synergistic mixture of a phosphate salt of an N-alkyl-diaminoalkane and a phosphate salt of an alkyl-monoamine.
  • the novel blend of the present invention comprises a mixture of a phosphate salt of an N-alkyldiaminoalkane and a phosphate salt of an alkyl-monoamine.
  • each of these types of salts has been proposed separately for use as additives to gasoline.
  • a mixture of these phosphate salts of amines which may be considered as somewhat related chemically, would produce results, both as to anti-icing and as to detergency, exceedingly beyond the results obtained by using either of these salts separately.
  • the phosphate salt is an alkyl phosphate salt.
  • Any suitable alkyl phosphate is used in preparing the amine salts and may be the: same or different in preparing the diamine salt and the monoamine salt.
  • the a-lkyl acid phosphate includes both the alkyl acid orthophosphates and the alkyl acid pyrophosphates. In the alkyl acid orthophosphates, the mono-alkyl ester, dialkyl ester or a mixture thereof may be employed.
  • the monoalkyl ester, dialkyl ester, trialkyl ester or mixtures thereof may be employed, the dialkyl ester being preferred, and the ester groups may be attached to the same or different phosphorus atom. Generally, however, this compound will be symmetrical and, thus, the alkyl ester groups will be attached to different phosphorus atoms.
  • alkyl acid orthophosphate and pyrophosphates are set forth below.
  • alkyl moiety contains from about 3 to about '20 and more particularly from about 4 to about 15 carbon atoms each.
  • particularly preferred alkyl acid orthophosphates include monobutyl acid orthophosphate, dibutyl acid orthophosphate, mixture of monoand dibutyl acid orthophosphates, monopentyl acid orthophosphate, dipentyl acid orthophosphate, mixture of monoand dipentyl acid orthophosphates, monohexyl acid orthophosphate, dihexyl acid orthophasphate, mixture of monoand dihexyl acid orthophosphates, monoheptyl acid orthophosphate, diheptyl acid orthophosphates, mixture of monoand diheptyl acid orthophosphates, monooctyl acid orthophosphate, dioctyl acid orthophosp'hate, mixture of monoand dioctyl acid orthophosphate
  • Preferred alkyl acid pyrophosphates include monobutyl acid pyrophosphate, dibutyl acid pyrophosphate, mixture of monoand dibutyl acid pyrophosphate, monopentyl acid pyrophosphate, dipentyl acid pyrophosphate, mixture of monoand dipentyl acid pyrophosphates, monohexyl acid pyrophosphate, dihexyl acid pyrophosphate, mixture of monoand dihexyl acid pyrophosphates, monoheptyl acid pyrophosphate, diheptyl acid pyrophosphate, mixture of monoand diheptyl acid pyrophosphates, monooctyl acid pyrophosphate, dioctyl acid pyrophosphate, mixture of monoand dioctyl acid pyrophosphates, monononyl acid pyrophosphate, dinonyl acid pyrophosphate, mixture of monoand dinonyl acid pyrophosphates,
  • alkyl acid phosphates including both the orthoand pyrophosphates, are manufactured commercially as a mixture of monoand dialkyl acid phosphates and are available commercially at a considerably lower cost. In many cases, such mixtures are very suitable for use in preparing the salt of the present invention and such use, therefore, is preferred for economic reasons.
  • alkyl acid phosphates are preferred, it is understood that other suitable phosphates may be employed but not necessarily with equivalent results.
  • an unsaturated aliphatic group may be employed, and thus may contain a double bond in the aliphatic chain,
  • the alkyl moiety or moieties may be replaced by cyclic derivatives including particularly cyclohexyl, but may comprise cyclobutyl, cyclopentyl, cycloheptyl,
  • aliphatic or cyclic groups may contain hydrocarbyl or non-hydrocarbyl substituents attached thereto, the last mentioned being selected from hydroxy, alkoxy, etc.
  • alkyl monoamine is used in preparing the alkyl phosphatesalt of alkyl monoamine for use as one component of the additive mixture of the present invention.
  • the alkyl monoamine may contain from about 3 to about 20 carbon atoms and preferably contains from about 4 to about 12 carbon atoms and thus includes butyl amine, pentyl amine, hexyl amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine, etc. It is understood that the alkyl moiety may be of straight or branched chain and may be of primary, secondary or tertiary configuration.
  • a particularly preferred alkyl monoamine for use in the present invention is 2-ethylhexyl amine.
  • Other preferred alkyl monoamines include those known as beta amines in which the alkyl group is attached to the nitrogen atom through the beta carbon atom of the alkyl group.
  • any suitable diamine is used in preparing the alkyl phosphate salt for use as a component in the additive mixture of the present invention. While the diamine may contain from about 3 to about 40 carbon atoms, it preferably contains from about 8 to about 20 carbon atoms.
  • a particularly preferred diamine is N-alkyl diaminoalkane in which the alkyl moiety contains from about 3 to about 30 carbon atoms and more particularly from about 6 to about 20 carbon atoms and the alkane moiety contains from about 2 to about 12 carbon atoms and preferably from about 3 to about 6 carbon atoms.
  • N-alltyl diaminoalkane is N-alkyl-l,3- diaminopropane, the alkyl group being derived from tallow.
  • This compound is available commercially under the trade name of Duomeen T.
  • Other preferred N-alkyl- 1,3-diaminopropanes comprise those in which the alkyl group is derived from lauric acid, coconut fatty acid, soya fatty acid, etc. These are available commercially at the present time and comprise mixed alkyl-substituted 1,3- diaminopropanes.
  • the alkyl group contains from about 12 to 20 carbon atoms per group and mostly contain 16 to 18 carbon atoms.
  • the alkyl group of the N-alkyl-1,3-diaminopropanes or other N-alkyl-diaminoalkanes may be prepared to contain any number of carbon atoms desired in the alkyl group and, thus, is selected from hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.
  • alkyl and alkane moieties may be of straight or branched chain.
  • alkyl moiety may be of primary, secondary or tertiary configuration.
  • particularly preferred in this embodiment are the beta amines in which the alkyl groups are attached to the nitrogen atoms through the beta carbon atoms of the alkyl groups.
  • N-alkyl-1,3-diamin0propanes are preferred it is understood that other suitable N-alkyl diaminoalkanes may be employed.
  • Illustrative examples include N-alkyl-1,2 diaminoethanes, N-alkyl-l,2 diaminopropanes, N-alkyl-l,Z-diaminobutanes, N-alkyl-l,3-diaminobutanes, N-alkyl-l,4-diaminobutanes, N-alkyl-1,2-diaminopentanes, N-alkyl-1,3-diaminopentanes, N-alkyl-l,4-diaminopentanes, N-alkyl-1,5-diaminopentanes, N-alkyl- 1,2-dia-minohexanes, N-alkyl-l,3-diaminohexanes, N-
  • alkyl-monoamine and/or alkyl-diaminoalkane may contain a double bond in the alkyl group.
  • the alkyl group may contain non-hydrocarbyl substitutions, the substitutions being selected from hydroxy, alkoxy, N-dihydrocarbylamide, halogen, particularly chlorine and fluorine, etc.
  • the amine in place of an aliphatic group, may be a cyclic amine as, for example, cyclohexyl amine, dicyclohexyl amine, and cyclohexyldiaminoalkane or the cycloalkyl group may be cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, etc.
  • the cyclic group may be a heterocyclic nitrogen compound including piperidyl, piperazyl, etc. It is understood that the different amines are not necessarily equivalent.
  • the neutral salts of the alkyl phosphate and alkyl monoamine and of the alkyl phosphate and diamine are preferred.
  • the neutral salts are prepared by utilizing stoichiometric amounts of the acid and the amine.
  • concentration of the alkyl acid phosphate and of the alkyl monoamine or of the alkyl acid phosphate and of the diaminoalkane will be selected so that there will be an equivalent number of acid groups to amino groups.
  • the specific concentrations will depend upon whether the orthophosphate or pyrophosphate or whether the monoalkyl phosphate or dialkyl phosphate are used. It also will depend upon whether the monoamine or diamine is employed.
  • the salt is a basic salt which is prepared by utilizing a deficiency of acid groups in relation to the amino groups.
  • the acid salt is used, which is prepared by using an excess of acid groups with relation to the amine groups. It is understood that these different salts are not necessarily equivalent. From the above description it will be seen that a number of different salts may be used in accordance with the present invention. It is understood that these different salts are not necessarily equivalent in the same fuel but all of them will serve to give in most, if not all, fuels improved results over those obtained through the use of each of the components individually.
  • the salts are prepared in any suitable manner and in general, are prepared by mixing the alkyl phosphate and the alkyl monoamine and/or diaminoalkane in the required proportions at ambient temperature, preferably with vigorous stirring.
  • the phosphate salt of the monoamine and the phosphate salt of the diamine may be separately prepared and utilized as such or subsequently mixed to prepare a blended composition.
  • the salts are readily prepared at room temperature, although slightly elevated temperature which generally will not exceed about 200 F. may be employed when desired. Excessive temperatures should not be allowed in order to avoid the undesired formation of reaction products resulting in the liberation of water and in the formation of phosphor amidic acid derivatives or other undesired reaction products.
  • a solvent in order to form a more fluid final product.
  • Any suitable solvent may be used and generally will comprise an organic compound and more particularly a hydrocarbon distillate.
  • Particularly preferred solvents are aromatic hydrocarbons including benzene, toluene, xylene, ethylbenzene, cumene, etc., or mixtures thereof, or parafiinic hydrocarbons including pentane, hexane, heptane, octane, nonane, decane, etc., or mixtures thereof, or mixtures of the aromatic and paraffinic hydrocarbons.
  • the phosphate salt of monoamine and the phosphate salt of diamine may be prepared separately or in admixture.
  • the salts may be blended to form an additive composition or the salts may be added separately to the substrate.
  • the different salts will be used in a proportion to produce improved anti-icing and detergency. This may range from 5% to 95% of one salt and 5% to 95% by weight of the other salt.
  • the phosphate salt of the diamine is used in a larger proportion and, in such cases, the salt of the diamine is used in a concentration of from about 60% to about by Weight and the phosphate salt of the monoamine is used in a concentration of from about 10% to about 40% by Weight, exclusive of solvent.
  • a stock solution may be prepared to contain the active ingredients in a concentration of from about 10% to a saturated solution which will be above 50% by weight of active ingredients.
  • the amount of the additive composition or the total of the two salts when added separately to gasoline or other carbureted engine fuel will be sufficient to effect improved deicing and improved detergency.
  • concentration should be as low as practical and thus may range from 0.001% up to 0.05% by weight and preferably is within the range of from about 0.00Q% to about 0.01% by weight of the fuel, based on active ingredients.
  • each of the salts may be added separately to the fuel or preferably are formed as a blend in a suitable solvent and incorporated in the fuel in this manner, preferably with intimate mixing to obtain uniform distribution throughout the fuel.
  • the mixture of salts of the present invention may be used along with other additives; added to the fuel for specific purposes including, for example, antioxidants, metal deactivators, etc.
  • these other additives may be blended with the salts of the present invention and the mixture marketed as a single commodity of multiple purposes.
  • these salts also serve to retard corrosion of the automotive parts through which the gasoline passes.
  • Still another advantage to the present invention is in the detergent action being effective to some degree beyond the carburetor, thus resulting in a cleaner intake manifold and less deposit on the intake valves.
  • Example I The additive mixture of this example comprises 75% by weight of the mixed monoand diiszooctyl acid orthophosphate salts of N-tallow-1,3-diaminapropane and 25% by weight of the mixed monoand ditridecyl acid orthophosphate salts of Z-ethylhexyl amine. These salts were each separately prepared by intimately mixing the phosphates and amines in proportions to form the neutral salts and then blending them with xylene solvent to form a final solution containing the active ingredients in a concentration of 50% by Weight.
  • a Dry Ice container was maintained one-half full at all times and was attached to the canburetor bowl in order to maintain constant fuel temperature and to prevent the loss of light ends of the fuel.
  • a surge chamber of a volume approximately equal to the cylinder displacement was installed between the carburetor and the engine, with the manifold vacuum being controlled by a valve ahead of the surge chamber.
  • Saturated air was obtained by passing the air through a modified CFR ice tower and thence over a water sump. The temperature of the water in the sump could be controlled so that saturated air at the temperature of the water results.
  • the air was pressurized to approximately 3.0 inches water to insure positive flow through the tower.
  • the saturated air temperature was varied in 25 F.
  • the expected time would be the average of 9.8 and 12.8, or 11.3 seconds but instead, surprisingly, the blend resulted in a time of 62.4 seconds.
  • the expected time would be the average of 27 and 46, or 37 seconds but instead was 152.1 seconds.
  • Example II The detergency properties of the additives were evaluated in a six cylinder Chevrolet 235 engine in which the standard cast iron caburetor throttle body was replaced by a section of transparent Plexiglas tubing upon which deposits form and can be inspected visually and, when desired, can be photographed.
  • the carburetor air is supplied from the room through an air cleaner and inducted into the air stream along with heated blowby and a small amount of exhaust gas.
  • the engine is operated for five hours on a speed cycle of two minutes at 500 rpm. and one minute at 1500 rpm. all with no load.
  • deposit formation occurs on the throttle body.
  • the throttle body is inspected visually and the results are reported as very dirty, dirty, moderate and clean.
  • the very dirty designation indicates that the throttle body is very heavily coated on the inside.
  • the dirty designation indicates heavy coating.
  • the designation of moderate means that there is a definite but lesser coating.
  • the designation of clean indicates that there is very little deposit coating on the throttle body.
  • the evaluations of this example were made using a gasoline having a boiling range of from 124 to 424 F., an API graivty at 60 F. of 54.5 and a Reid vapor pressure of 5.1 p.s.i.
  • the following table reports evaluations made in the manner described above when using samples of the gasoline without additive, samples of the gasoline containing the phosphate salt of the monoamine, samples of the gasoline containing the phosphate salt of diaminoalkane, and samples of the gasoline containing the mixture of phosphate salts described in Example I.
  • the additives when employed, were used in a concentration of 50 parts per million of the 50% solution. In the case of the blend, the toal concentration of active ingredients was 25 parts per million.
  • Example III The blend of this example is a mixture of 75% by weight of the mixed monoand ditridecyl acid phosphate salts of N-tallow-1,3-diaminopropane and 25% by weight of mixed monoand ditridecyl acid phosphate salts of n-heptyl-beta amine.
  • the carbon atoms are in straight chain arrangement and the amino nitrogen is attached to the beta or second carbon atom.
  • Example IV The additive blend of this example is a mixture of 25% by weight of the mixed monoand ditridecyl acid phosphate salts of N-tallow-1,3-diaminopropane and 75% by Weight of the mixed monoand ditridecyl acid phosphate salts of n-heptyl-beta amine.
  • Example V The salt of this example is a blend of 60% by weight of the diamyl acid phosphate salt of N-oleyl-l,3-diaminopropane and 40% by weight of diamyl acid phosphate salt of oleyl amine.
  • the salt was prepared by intimately mixing at room temperature two equivalents of the diamyl acid phosphate with one equivalent each of N- oleyl-1,3-diaminopropane and oleyl amine. Toluene solvent was used in the mixing in a concentration to form a final solution of 40% by weight of active ingredients.
  • the blended additive mixture solution prepared as described in the above manner, is incorporated in commercial gasoline in a concentration of 60 parts per million and serves to prevent engine stalling and to maintain cleanliness of the carburetor throttle body.

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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)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US454167A 1965-05-07 1965-05-07 Synergistic additive mixture Expired - Lifetime US3425815A (en)

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US (1) US3425815A (xx)
BE (1) BE680542A (xx)
CH (1) CH498925A (xx)
DE (1) DE1545508B1 (xx)
DK (1) DK117118B (xx)
ES (1) ES326413A1 (xx)
GB (1) GB1139186A (xx)
NL (1) NL6606121A (xx)
SE (1) SE339771B (xx)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639110A (en) * 1968-12-02 1972-02-01 Marathon Oil Co Detergent gasoline composition
WO1995020592A1 (en) * 1994-01-29 1995-08-03 Castrol Limited Anti-wear additives and their use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005033253A1 (de) * 2003-10-07 2005-04-14 Swiss E-Technic Ag Schwefelarmes öl, verfahren zur senkung der aggressivität eines solchen öls

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848414A (en) * 1955-11-23 1958-08-19 Universal Oil Prod Co Corrosion inhibitor
US2863742A (en) * 1954-10-04 1958-12-09 Gulf Oil Corp Gasoline fuel compositions
US2863904A (en) * 1955-05-09 1958-12-09 Gulf Oil Corp Amine salts of di oxo-octyl orthophosphates
US3063820A (en) * 1959-05-18 1962-11-13 Universal Oil Prod Co Stabilization of hydrocarbons

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130018A (en) * 1962-09-12 1964-04-21 Du Pont Anti-stalling composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2863742A (en) * 1954-10-04 1958-12-09 Gulf Oil Corp Gasoline fuel compositions
US2863904A (en) * 1955-05-09 1958-12-09 Gulf Oil Corp Amine salts of di oxo-octyl orthophosphates
US2848414A (en) * 1955-11-23 1958-08-19 Universal Oil Prod Co Corrosion inhibitor
US3063820A (en) * 1959-05-18 1962-11-13 Universal Oil Prod Co Stabilization of hydrocarbons

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639110A (en) * 1968-12-02 1972-02-01 Marathon Oil Co Detergent gasoline composition
WO1995020592A1 (en) * 1994-01-29 1995-08-03 Castrol Limited Anti-wear additives and their use
AU682748B2 (en) * 1994-01-29 1997-10-16 Castrol Limited Anti-wear additives and their use

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DE1545508B1 (de) 1971-01-14
BE680542A (xx) 1966-10-17
GB1139186A (en) 1969-01-08
ES326413A1 (es) 1967-07-01
NL6606121A (xx) 1966-11-08
DK117118B (da) 1970-03-16
CH498925A (de) 1970-11-15
SE339771B (xx) 1971-10-18

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