US2496930A - Composition useful as gum inhibitor for motor fuels - Google Patents

Composition useful as gum inhibitor for motor fuels Download PDF

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Publication number
US2496930A
US2496930A US682248A US68224846A US2496930A US 2496930 A US2496930 A US 2496930A US 682248 A US682248 A US 682248A US 68224846 A US68224846 A US 68224846A US 2496930 A US2496930 A US 2496930A
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United States
Prior art keywords
inhibitor
aniline
dipda
effectiveness
gum
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Expired - Lifetime
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US682248A
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English (en)
Inventor
Marshall R Brimer
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE474374D priority Critical patent/BE474374A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US682248A priority patent/US2496930A/en
Priority to FR1034555D priority patent/FR1034555A/fr
Priority to GB18203/47A priority patent/GB631839A/en
Application granted granted Critical
Publication of US2496930A publication Critical patent/US2496930A/en
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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 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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
    • C10L1/103—Liquid carbonaceous fuels containing additives stabilisation of anti-knock agents

Definitions

  • This invention relates to a composition useful as a gum inhibitor for motor fuels and to motor fuels stabilized against gum formation.
  • the inhibitor should be a liquid, in order to permit ready blending with the motor fuel.
  • DIPDA N,N'diisopropyl p phenylenediamine
  • a suitable solvent e.g. isopropyl alcohol or toluene.
  • the gum inhibitor effectiveness of solutions of DIPDA in these commonly employed solvents is directly proportionalA to the concentration of the DIPDA 7 Claims. (Cl. 252-401) in solution, the solvent having substantially no gum inhibitor effectiveness.
  • I mix t ⁇ gether to give an intimate mixture or solution, at least one N,N'dialkyl-p-phenylenediamine, e. g. N,N diisopropyl p phenylenediamine, N,N'disecondary butyl p phenylenediamne, etc., and at least one primary aromatic monoamine of the benzene series, e. g. aniline, a toluidine, a xylidine, etc.
  • the primary aromatic monoamine of the benzene series constitutes from about 0.5 to about by weight of the mixture.
  • Primary aromatic monoamines of the benzene series containing only carbon, hydrogen and of aniline.
  • nitrogen atoms are advantageously employed.
  • the resulting mixture vis advantageously dissolved in a solvent before blending with the motor fuels.
  • Typical solvents include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl alcohols,v n-propyl ethyl ether, n-propyl isopropyl ether, diisopropyl ether. di-n-propyl ether, benzene, toluene, xylenes, heptane, mixtures of petroleum hydrocarbons, e. g. straightrun gasoline, etc.
  • These solvents are inert solvents, i. e. they have substantially no gum inhibitor eectiveness, in and of themselves and substantially no synergistic effect on the Kurs inhibitor effectiveness of the N,N'dialkylp phenylenediamines.
  • the DIPDA solutions in aniline possess effectiveness far in excess of that calculated by multiplyingthe effectiveness of pure DlPDA by the concentration of DIPDA in the aniline solution, yet the effectiveness of aniline alone as a sum inhibitor is less than 0.05.
  • Curve B in Fig. 1 of the accompanying drawing gives the eectiveness of solutions of DIPDA in aniline in the same standard reference gasoline, and it will be seen that curve B departs greatly'in a positive direction from curve A.
  • the shape of curve B can be explained if the presence of aniline enhances the effectiveness of DIPDA, or if DIPDA enhances the eiectiveness
  • the unexpected nature of my discovery can be more clearly understood if the difference between curve B and curve A is ascribed to inhibitor effectiveness exerted by aniline in the aniline solutions of DIPDA.
  • the diilerence between curve A and curve B represents the 'inhibitor effectiveness contributed by the aniline in the solution.
  • the quotient represents the apparent inhibitor eectiveness of the aniline in the solution. Representative values are as follows:
  • aniline when aniline is mixed vwith DIPDA, the effectiveness of the aniline appears to increase from less than 0.05 to more vthan 1.80, an increase of more than 3600 per cent.
  • a practical inhibitor should be liquid, in order to facilitate blending with the motor fuels. Not only should thevinhibitor be liquid, but the liquidfshouldfnot be susceptible to freezing at temperatures normally encounteredin retlnerles, and if the j inhibitor is .susceptible tofreezing above 10 C., its freezl ing point may.' handicap its practicability.v
  • solutionsV being grouped laccording to inhibitor eectiveness.
  • the iirstfour columns of Table I show the ⁇ composition of the solutions which were tested, the fifth column shows the effectiveness of the solutions, and the sixth column shows the,
  • Table I shows that if it-be desired to 'maintain a lcertain maximum freezing"4 point,the effectiveness can be greatly increased.
  • 10-C.' is set as the maximum practical allowablev freezing point, without using aniline, the attainable eil'ectiveness is 0.9 l ⁇ (45% DIPDA+ ⁇ 55% toluene, freezing point 9 C.) or 0.7 (3,5% DIPDA-,-65% isopropyl alcohol. freezing pointe C.) but by using my invention, the ⁇ attainableeffectiveness ⁇ .can be raised to 1.4',(either"53%-DIPDA-20% isopropyl alcohol-27% aniline, ⁇ freezing point 10 C. or
  • gum 50% to 37% a saving of 26% of the most exinhibitors prepared according to my invention pensive component of the solution.
  • inert' solvents the same 20% separation temperature" or a 76 have been replaced by 21% of aniline without line.
  • Yet another important advantage to be derived from the use of my invention is the improvement ⁇ rwhich can be attained with respect to color sta- Y bility.
  • the color stability of the inhibitor is important from the standpoint of practical use. Inhibitor and inhibitor solutions commonly are in contact with air before and after addition to motor fuels If an inhibitor under consideration is found to produce strong color upon atmospheric oxidation, it is said to lack color stability, and if it does not produce deep color upon atmospheric oxidation, it is said to be color-stable. Inhibitors which show color instability are ordinarily not suitable for practical use because the color produced interferes with the saleability of the motor fuel.
  • an inhibitor by observing the shade and depth of color produced when one ounce of fresh inhibitor is allowed to stand in a Z-ounce bottle, in the neck of which is fitted a stopper bearing a, 1-inch length of 0.5 mm. tubing to permit access of air to the interior of the bottle. If a strong color developsupon a few hours exposure. the inhibitor is unsatisfactory for practical use, while if the inhibitor merely darkens after standing several days, it is satisfactory for practical use.
  • DIPDA has not been used commercially as an inhibitor because of the fact that it lacks color stability when dissolved in solvents commonly used in the art.
  • An isopropyl alcohol solution of DIPDA becomes very dark in color after only a few hours, even though the exposure of the solution to atmospheric oxygen has been slight.
  • solutions of DIPDA in isopropyl alcohol and aniline are color-stable for several days, even when exposed continuously to atmospheric oxygen by the procedure described above. As little as aniline in the solution is adequate to provide color stability and, since larger proportions of aniline are desirable in order to take full advantage of my invention with regards to other desirable properties described herein, color stability is no longer a problem with DIPDA when my invention is used.
  • curves C and D in Figure 2 of the accompanying drawing show the effectiveness of DIPDA solutions in inert solvents, such as, isopropyl alcohol and toluene compared with solutions of DIPDA in o-toluidine.
  • the other important properties such as, freezing point, 20% separation temperature, and color, as well as cost, are improved 'by the use of o-toluidine in the manner similar to aniline.
  • the xylidines are likewise effective when used in accord-ance with my invention.
  • compositions comprising a mixture of at least one N.Ndisecondary alkyl-p-phenylenediamine and at least one primary aromatic monoamine ofthe benzene series which contains only carbon, hydrogen and nitrogen atoms, those in which the nmonoamine constitutes from about l5A to 45% by weight of the mixture are especially Such compositions are advantageously containing from about 20 to about 45% by weight of the inert solvent.
  • My invention is directed to the stabilization of hydrocarbon motor fuels against deterioration.
  • hydrocarbon motor fuel I mean not only motor fuels constituted entirely of hydrocarbons but also motor fuels containing hydrocarbon and appreciable amounts of other combustible substances, such as alcohols.
  • Cracked gasoline as is well known, has an undesirable tendency to undergo deterioration upon storage.
  • Straight-run gasolines on the other hand, do not have the same undesirable tendency to deteriorate, although blended stock containing cracked gasoline and straight-run gasoline usually show thel undesirable tendency to deteriorate. It is to the stabilization of any unstable liquid motor fuels comprising light hydrocarbons and normally tending to deteriorate that my invention is directed.
  • I dissolve a small amount of the composition in the motor fuel.
  • an amountsufllcient to give a concentration of from about 0.000l% to about 0.1% (by weight) of the composition in the motor fuel will suflice to give a motor fuel of suitable stability against deterioration.
  • the quantity of any one of my new compositions which is actually employed will depend upon the nature of the motor fuel being stabilized and the conditions under which the fuel is stored.
  • the tendency of the motor fuel to'form gum can be determined among other methods by an accelerated oxidation test. The test described by Egloff et al., supra, is very satisfactory and is widely used.
  • An induction period of less than 75 minutes is usually indicative of very low stability, while an induction of 300 or more minutes, for freshly made motor fuels, represents a fuel possessing suitable stability for from 6 to 12 months storage in the northern half of the United States. For more southern or Warmer climates, the induction period should be increased somewhat for satisfactory bulk storage of about one year duration.
  • My new composition can be employed to retard gun formation in hydrocarbon motor fuels which tend to undergo deterioration whether the motor fuel contains small or large amounts of addition agents, such as tetraalkyl lead compositions. It is, of course, known that tetraalkyl lead compounds, such as tetraet-hyl lead, are added to hydrocarbon motor fuels to improve the octane rating of the motor fuels.
  • tetraalkyl lead compound In some cases only a relatively small amount of the tetraalkyl lead compound is added, but sometimes with certain aviation grades of gasoline, a larger amount is used, such as with aviation gasoline having an octane number above 80 and comprising essentially non-gum-forming yhydrocarbons containing less than 1% by volume of oleflnic or diolenic hydrocarbons. Motor fuels having a relatively large amount of tetraalkyl lead compounds are usually referred to as heavily leaded gasoline.
  • Ethyl fluid usually is a solution containing a mixture of tetraalkyl lead compound and a halogenated hydrocarbon, such as ethylene dibromide or ethylene dichloride, or both.
  • My new compositions serve to retard the formation of haze in ethyl fluid or in hydrocarbon motor fuels containing the "ethyl fluid, whether the hydrocarbon motor fuel is one which forms gum upon storage or is one which is composed essentially of non-gum-forming hydrocarbons.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of a N,Ndi secondary alkyl-p-phenylenediamine in which each alkyl group contains from 3 to 4 carbon atoms and a primary aromatic amine selected from the group consisting of aniline and o-toluidine, the primary aromatic amine constituting 10 from about 0.5 to about by weight of the mixture.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,Ndi isopropyl-p-phenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by weight of the mixture.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,N'di secondary butyl-p-phenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by weight of the mixture.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,N'di isopropyl-pphenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by weight of the mixture, the mixture being dissolved in an inert solvent.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,N'di isopropyl-p-phenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by Weight of the mixture, the mixture being dissolved in isopropyl alcohol.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,N'di isopropyl-p-phenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by weight of the mixture, the mixture being dissolved in toluene.
  • a composition useful as a gum inhibitor for motor fuels consisting of a mixture of N,N'-di secondary butyl-p-phenylenediamine and aniline, the aniline constituting from about 0.5 to about 85% by weight of the mixture, the mixture being dissolved in an inert 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
US682248A 1946-07-09 1946-07-09 Composition useful as gum inhibitor for motor fuels Expired - Lifetime US2496930A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE474374D BE474374A (en(2012)) 1946-07-09
US682248A US2496930A (en) 1946-07-09 1946-07-09 Composition useful as gum inhibitor for motor fuels
FR1034555D FR1034555A (fr) 1946-07-09 1947-07-08 Nouvelles compositions utilisables pour stabiliser les carburants pour moteurs
GB18203/47A GB631839A (en) 1946-07-09 1947-07-09 Inhibitors for motor fuels

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US682248A US2496930A (en) 1946-07-09 1946-07-09 Composition useful as gum inhibitor for motor fuels

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2700612A (en) * 1951-01-31 1955-01-25 Universal Oil Prod Co Stabilization of organic materials
DE929806C (de) * 1950-05-25 1955-07-04 Ici Ltd Antioxydationsmittel
US2734808A (en) * 1956-02-14 P-phenylenediamine gasoline stabilizers
US2742349A (en) * 1952-02-25 1956-04-17 Ethyl Corp Synergistic stabilizing compositions
US2796336A (en) * 1953-03-23 1957-06-18 Ethyl Corp Synergistic antioxidant composition and use
US3053682A (en) * 1959-10-30 1962-09-11 Universal Oil Prod Co Stabilization of hydrocarbons
US20040216371A1 (en) * 2003-04-29 2004-11-04 Colket Meredith Bright Nitrogen in fuel-additives to suppress particulate emissions from gas turbines and diesel engines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB385593A (en) * 1930-03-25 1932-12-29 Du Pont Improvements in or relating to fuel oils
US2323948A (en) * 1940-11-06 1943-07-13 Eastman Kodak Co Process for preparing phenylenediamine derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB385593A (en) * 1930-03-25 1932-12-29 Du Pont Improvements in or relating to fuel oils
US2323948A (en) * 1940-11-06 1943-07-13 Eastman Kodak Co Process for preparing phenylenediamine derivatives

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734808A (en) * 1956-02-14 P-phenylenediamine gasoline stabilizers
DE929806C (de) * 1950-05-25 1955-07-04 Ici Ltd Antioxydationsmittel
US2700612A (en) * 1951-01-31 1955-01-25 Universal Oil Prod Co Stabilization of organic materials
US2742349A (en) * 1952-02-25 1956-04-17 Ethyl Corp Synergistic stabilizing compositions
US2796336A (en) * 1953-03-23 1957-06-18 Ethyl Corp Synergistic antioxidant composition and use
US3053682A (en) * 1959-10-30 1962-09-11 Universal Oil Prod Co Stabilization of hydrocarbons
US20040216371A1 (en) * 2003-04-29 2004-11-04 Colket Meredith Bright Nitrogen in fuel-additives to suppress particulate emissions from gas turbines and diesel engines

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Publication number Publication date
BE474374A (en(2012))
GB631839A (en) 1949-11-10
FR1034555A (fr) 1953-07-27

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