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, 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
  • C10L1/22—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
• • 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
  • C10L1/22—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
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

• Alkenyl succinic acid anhydrides of the corresponding acids are utilizable in S.N. 124,031.
• the general structural formulae of these compounds are: wherein R is an alkenyl radical.
• the alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydorgen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein.
• an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical.
• an alkenyl succinic acid anhydride or the corresponding acid must be used.
• Succinic acid anhydride and succinic acid are not utilizable herein.
• the reaction product produced by reacting with succinic acid anhydride is unsatisfactory.
• the alkenyl succinic acids also react, in accordance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the remaval of water formed during the reaction and also often causes undesirable side reactions to occur to some extent.
• alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term "alkenyl succinic acid anhydride” is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore.
• Non-limiting examples of the alkenyl succinic acid anhydride reactant are ethenyl succinic acid anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid, 2-methyl-butenyl succinic acid anhydride; 1,2-dichioropentyi succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2-ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-dioctyl succinic acid; octenyl
• alkenyl succinic acid anhydrides of S.M. 124,031 are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difficult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relating pure anhydrides, are utilizable herein. Corresponding alkyl succinic anhydrides can also be employed, i.e., where the alkenyl group is saturated in any of the above instances, the preparation of alkyl succinic acids and anhydrides thereof is well known to the art.
• the etherdiamine of S.N. 124,031 has the general formula ROANH A'NH 2 where R is an alkyl group having about 1 to 18 carbons, such as from about 5 to 13 carbons, for example from about 8 to 10 carbons. but preferably about 8-9 carbons.
• a and A' which may be the same or different alkylene group, having about 2 to 10 carbons such as about 2 to 5 carbons, but preferably 3 carbons.
• the preferred etherdiamine is CH 3 (CH 2 ) 7 - S O(CH 2 ) 3 NH(CH 2 ) 3 NH 2
• the reaction products are prepared by mixing the components together at ambient temperature. Since the reaction is exothermic, cooling may be desirable in larger batches.
• the molecular weight of tetrapropenyl succinic acid is 284 and CH 3 (CH 2 ) 7 CH 2 0(CH 2 ) 3 NH(CH 2 ) 3 NH 2 is 258.
• the stoichiometrical weight ratio of AASA to EDA is about 1.1 to 1.
• the most effective AASA to EDA weight ratio is in excess of 1.1 to 1, with an optimum of about 3 to 1 or greater.
• the AASA to EDA weight ratio can be for example from about 10 to 1, such as from about 8 to 1, but preferably from about 6 to 1, with an optimum of about 3 to 1.
• reaction product contains an excess of AASA.
• oxygenated fuels such as alcohol have been employed as fuels, either alone, or in combination with petroleum products.
• oxygenated fuels include ethanol, methanol, tertiary butyl alochol (TBA), methyl tertiary butyl ether (MTBE) or mixtures thereof, which are incorporated into the fuel as fuel extenders, octane boosters or both.
• compositions of S.N. 124,031 are excellent corrosion inhibitors for oxygenated fuel systems.
• Gasohol and other oxygenated fuels present at least one special problem. That is if water is mixed with gasohol a clear solution results up to about 0.5 to 0.7% (depends upon fuel temperature and aromatic content of the gasoline.) When the critical amount of water is exceeded a phase separation occurs. The separate phase contains both water and ethanol. In addition to the obvious potential problem of poor operability should this aqueous phase enter the fuel systems of vehicles is the concern (supported by some evidence) that this water/ethanol phase is quite corrosive. The compositions of the present invention are useful in solving this problem.
• compositions of S.N. 124,031 have been widely tested to prove their usefulness. These tests are summarized as follows:
• Composition B (ether diamine) EDA (7-9)
• Composition F (MFGA)
• Gasoline 1-A Unleaded regular gasoline
• Gasoline 1-B 90% gasoline 1-A, 10% Fuel grade ethanol (gasohol)
• Gasoline 1-C 95% gasoline 1-A, 2.5% methanol 2.5% Tertiary butylalcohol (i.e. 5% OxinolTM)
• Gasoline 1-D 90% gasoline 1-A, 10% Methyl tertiary butyl ether (i.e. 10% MTBE)
• Gasoline 1-E 93% gasoline 1-A, 7% Tertiary butyl alcohol (i.e. 7% TBA)
• Gasoline 2-A No lead regular gasoline
• Gasoline 2-B 90% gasoline 2-A, 10% Fuel grade ethanol (gasohol)
• Gasoline 3 Leaded regular gasoline
• a six-cylinder 300 CID engine is operated for a total of 20 hours in a test stand. Power is absorbed by a momentum exchange water brake dynamometer. During the test period the engine is cycled between idle and cruise speed. The cycle is a ten-minute cycle with the idle and cruise phases being three minutes and seven minutes in duration respectively. Idle conditions of 700 RPM and 1.5% CO in the emissions under no load are set at the start of the test. Cruise conditions are maintained at 2000 RPM with 10BHP load throughout the test. A controlled amount of blowby is returned to the carburetor at all times and full EGR is applied during the cruise phase. Exhaust emissions are recorded. Temperatures and other parameters which affect or indicate eingine operation are measured and in some cases controlled. The weight of deposits formed on a removable throttle body sleeve is used to judge additive performance.
• This test is used to determine the corrosive effects of a water/ethanol phase on various metals that are in direct contact with this mixture.
• a polished metal coupon is totally immersed in a water/ethanol phase obtained by adding water to gasohol in an amount sufficient to extract ethanol into the aqueous phase.
• the sample is stored in the dark at room temperature.
• the coupon is visually inspected for evidence of corrosion and weight changes are also recorded.
• a one inch square metal coupon with a 7 inch centered hole is polished, rinsed in heptane then acetone, and dried. Initial coupon weight is then obtained.
• Two hundred (200) mls of gasohol are placed in an 8-ounce acid-cleaned jar. Twenty (20) mls of water are added to the gasohol and shaken thoroughly to effect the separation of a lower water/ethanol phase.
• the metal coupon is then suspended in the lower phase using a 1 ⁇ 4 inch glass rod with an enlarged and flattened end so that the coupon surface is totally immersed in the lower phase but off the bottom of the jar.
• the jar lid is sealed and the jar is placed in a dark environment. Visual inspections for evidence of corrosion are made periodically and a coupon weight change is recorded at the end of the test.
• the corrosion products, if any, are removed using a camel's hair bruch prior to obtaining a final weight.
• alkenyl succinic acids can also be employed such as by way of illustration and not of limitation polymeric alkenyl succinic acids such as those containing the following repetitive unit.
• R is a hydrocarbon group having at least about 8 carbons such as about 8 to 48 carbons, for example from about 12 to 42 carbons, but preferably from about 20 to 28 carbons.
• the hydrocarbon group is alkyl.
• amines can be employed in this invention. These include primary, secondary and tertiary monoamines, diamines, and polyamines.
• the amines have a total of about 6-40 carbons, for example from about 8 to 30 carbons, but preferably from about 10 to 18 carbons.
• the optimum number of carbons in the amine will depend upon the particular amine employed. In general, the optimum number of carbons is from about 8 to 30, but preferably from about 10 to 20.
• the amine has a hydrocarbon group which has a continuous carbon chain of at least about 6 carbons such as from about 6 to 34, for example from about 6 to 20, but preferably from about 6 to 14.
• the hydrocarbon group may be a straight, branched chain, or both.
• the amine may also have other elements present such as oxygen, etc.
• R N where R is the hydrocarbon group having at least about 6 carbon atoms and N is the rest of the amine.
• N may be a mono amine, a diamine or a polyamine or may contain other elements such as oxygen, etc. such as -( A) n NH 2 where A is alkylene, preferably -(CH) 2-3 and n is a zero or number such as 0-6, but preferably 1-3.
• Armeen 2C secondary high molecular weight aliphatic amines known as Armeen 2C can be used.
• Armeen 8D high molecular weight aliphatic amines known as Armeen 8D, Armeen 12D, Armeen 16D, Armeen C, Armeen 18D, Armeen CD, Armeen HTD, Armeen T, Armeen O.
• Suitable amines having an aromatic ring include alpha-methylbenzylamine and alpha-methylbenzyl- monoethanolamine.
• Amines having ring structures include aniline, diphenylamine, cyclohexylamine, dicyclohexylamine, and various comparable amines with alkyl substitutents in the ring.
• a monoamine compound can be cyclic or non-cyclic. Those which are cyclic may be heterocyclic as in the case of morpholine and its derivatives or oxazolines which may be regarded as derivatives of N-acyl-2-amino-ethanols. This would apply where instead of being a derivative of monoethanolamine the oxazoline was a derivative of a low molal acid or a high molal acid and 2-amine-2-methyl-1,3-propanediol.
• polyamines corresponding to the formula ?C 0, or greater (for example 1-10 or greater) in which R" is hydrogen, alkyl, cycloalkyl, aryl, or aralkyl and R' is a divalent radical such as
• suitable amines include: Ethylenediamine, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, Propylenediamine, Dipropylenetriamine, Tripropylenetetramine, Butylenediamine, Aminoethylpropylenediamine, Aminoethylbutylenediamine
• polyamines in which the nitrogen atoms are separated by a carbon atom chain having 4 or more carbon atoms include the following: Tetramethylenediamine, pentamethylenediamine, and especially hexamethylenediamine. and derivatives obtained by treating ethylenebisoxypropylamine with 1,2,3, or 4 moles of ethylene oxide, propylene oxide, butylene oxide, or the like.
• Other compounds including those having cyclic structures include piperazine, and the corresponding derivatives obtained by treating piperazines with alkylene oxides. The same applies to substituted piperazine such as the 2,5-dimethylpiperazine.
• Duomeen is a trademark designation for certain diamines.
• Duomeens have the following general formula: R is an alkyl group derived from a fatty acid or from the mixed fatty acids as obtained from certain oils.
• the specific Duomeen and the source of the radical R are as follows:
• compositions of this invention may be employed in any amount capable of inhibiting rust or corrosion, such as in minor amounts of at least 1 p.p.m., such as at least 5 p.p.m., for example 15 to 200 p.p.m., or more, but preferably 25-50 p.p.m.
• compositions of the invention may be desirable to add larger amounts of the compositions of the invention, such as up to about 100,000 p.p.m. or greater, for example from about 20 to 1,000 p.p.m.
• compositions of this invention inhibit corrosion in those systems where water is in the dissolved, suspended, or separate phase, including inhibition in the gasohol phase, as well as the separate water phase or separate water-alcohol phase.

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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)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Lubricants (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Citations (8)

• 1987
  • 1987-07-14 EP EP87306222A patent/EP0299119A1/fr not_active Withdrawn
  • 1987-07-22 BR BR8703124A patent/BR8703124A/pt unknown
  • 1987-07-31 JP JP19254087A patent/JPS6436691A/ja active Pending

Patent Citations (8)

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