US3051562A - Stabilized jet combustion fuels - Google Patents

Stabilized jet combustion fuels Download PDF

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US3051562A
US3051562A US3484A US348460A US3051562A US 3051562 A US3051562 A US 3051562A US 3484 A US3484 A US 3484A US 348460 A US348460 A US 348460A US 3051562 A US3051562 A US 3051562A
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mole
mixture
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grams
ester
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US3484A
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Paul V C Gee
Jr Harry J Andress
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ExxonMobil Oil Corp
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Socony Mobil Oil Co Inc
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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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • 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
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • 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
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups

Definitions

  • Another object of this invention is to provide a means for stabilizing jet combustion fuels against thermal degradation.
  • a further object is to provide jet combustion fuels having a greatly reduced tendency to foul heat exchange tubes and to plug injection nozzles.
  • a specific object is to provide jet combustion fuels containing an additive composition of certain esters
  • a more specific object is to provide jet combustion fuels containing the reaction product of certain partial esters with polyamines and hydroxyaromatic aldehyde.
  • the present invention provides an additive composition
  • an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a 1-olefin, having between about 2 carbon atoms and about carbon atoms per molecule, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of a primary or secondary aliphatic alcohol containing between about 4 carbon atoms and about 20 carbon atoms per molecule to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of a polyamine of the formula H N(RNH) -H,
  • R is ethylene or propylene and n is 1 or 2, and
  • the mixed monoand di-ester product used in the reaction products of this invention is the mixed mono and di-aliphatic ester of certain olefin-maleic anhydride heteropolyrners.
  • the heteropolymer is produced by copolymerizing equimolar amounts of a l-olefin and maleie acid anhydride.
  • the l-olefin reactant should contain between about 2 carbon atoms and about 20 carbon atoms per molecule.
  • the reactants are heated together, either in bulk, or in the presence of a suitable solvent, such as benzene, toluene, xylene, dioxane, or carbon tetrachloride, at temperatures varying between about C. and about 175 C.
  • the copolymerization is carried out in the presence of a peroxide catalyst, such as benzoyl peroxide.
  • a peroxide catalyst such as benzoyl peroxide.
  • the amount of peroxide used is between about one percent and about 5 percent, by weight of the reactants.
  • the time required to complete the copolymerization varies between about one hour and about 10 hours.
  • the mixed monoand di-aliphatic ester is made by esterifying the heteropolymer with a primary or secondary aliphatic alcohol containing between about 4 carbon atoms and about '20 carbon atoms per molecule.
  • the branched-chain alkyl alcohols are particularly preferred.
  • Non-limiting examples of the esterifying alcohols are butanol; Z-methylpropanol; 2,2'dirnethylpropanol; amyl alcohol; isoamyl alcohol; hexanol; hexenol; 3-methyl-' pentanol; Z-ethylhexanol; isodecanol; decanol; dodecanol; iso-tridecanol; hexadecanol; hexadecenol; octadecanol; octadecenol; and eicosanol.
  • the esters utilizable herein must be a mixed monoand dialiphatic ester. acted with the olefin-maleic anhydride in amounts of between about 1.5 moles and about 1.75 moles per mole of olefin-maleic anhydride copolymer.
  • the ester can be made by any of the known methods for preparing esters of carboxylic acids.
  • the mixed esters of l-olefin-maleic anhydride copolymers can be prepared by heating at 200 C., from 1 to 10 hours, one mole of l-olefin-maleic anhydride copolymer with 1.5-1.75 moles of alcohol with the elimination of 0.5 0.75' mole of water.
  • the esterification is suitably carried out in the presence of a catalyst, such as p-toluene sulfonic acid monohydrate or sulfuric acid.
  • the amount of p-toluene sulfonic acid monohydrate or sulfuric acid used is from 0.1 percent to 5 percent by weight of the reactants.
  • various techniques of esterification such as azeotropic distillation, or removal of water by the use of applied vacuum. It is to be understood that the particular method used to prepare the mixed ester component is of little importance to the additive compositions of this invention or to the jet combustion fuels containing them.
  • the mixed monoand di-aliphatic ester component is then further reacted with, per mole of mixed ester, between about 0.25 mole and about 0.5 mole of a polyamine reactant as hereinafter defined and between about 0.25 mole and about 0.5 mole of salicylaldehyde.
  • the polyamine reactant has the formula H N(RNH) -H, wherein R is ethylene or propylene and n is 1 or 2. Examples of the polyamine reactant are ethylenediamine,
  • the reaction between the copolymer ester, polyamine reactant, and salicylaldehyde is a condensation reaction accompanied by the formation of water of reaction. tures varying between about 90 C. and about C. and for a period of time varying between about one hour and about 5 hours, or until water of condensation ceases to form.
  • various techniques of esterification are equally applicable to the reaction with amine and salicylaldehyde.
  • the alcohol reactant is re-
  • the reaction is suitably carried out at temperawater can. be removed by azeotropic distillation.
  • Theliydrocarbon 'jet'fuels that are improved in accordance with this invention are hydrocarbon fractions having an initial boiling pointof at least about 100 F. and an end boiling point as high. as about 750 F. These fuels can be made up of straight-run. distillate fractions,
  • Theamount of additive composition, i.e. reaction product aforedescribed, that is added to the jet combustion fuels Will vary between about 0.001'percent and about onejpercent, by weight of the fuel, and preferably be-.-
  • the concentration of additive composition will vary between about 5.0
  • pounds per thousand barrels of fueland about 2000 pounds per thousand barrels of fuel Preferably, 'the concentration will vary between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousandbarrels of fuel.
  • Olefin A is a "mixture containing about 8.2 Weight percent 1-heXene,'about 7 weight percent 1'-decene, about'48 weight percent l-dodecene, about 17.5 weight percent l-tetradecene, about 8.8' weight percent .l-hexadecene, and about 10.5 weight percent l-octadecene.
  • V e 01efin.-B- is a mixture containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about weight percent.
  • 7 7 Alcohol C is a mixture of normal aliphatic, mono- V hydric'alcohols containing about 2.8 weight percent decanol, about '61 weight percent dodecanol, about 21 7 weight percent tetradecanol, about 11 Weight percent 7 hxadecanol, and about 2.2 weight percent octadecanol.
  • reaction prod- 7 not wasdiluted with 200 cc. of benzene, Water-washed and topped to 175 C. .under a pressure of 1.5 mm. of mercury- Example 3 A mixture, @115 grams (0.5 mole) of olefin B, 49
  • the mixture was refluxed at 90 C. for 3 hours and at 175 C. for 30 minutes.
  • the amount of water collected during the reaction was 4.5 cc., theory 4.5 cc.
  • the product was topped to 175C. under the house vacuum to remove the xylene.
  • Example 5 A mixture of 115 grams (0.5 mole) of olefin B, 49 grams (0.5 mole) of maleic anhydride, 1.65 grams (1%) of benzoyl peroxide and 30 cc. of xylene as diluent was gradually heated with stirring. Heat was turned oil at 100 C. The reaction was exothermic, and the temperature rose rapidly to 156 C., then dropped. The mixture was stirred at 150 C. for 4 hours to complete copolymerization. The copolymer was diluted with 150 cc. of toluene. To the copolymer was added at room temperature 175 grams (0.875 mole) of alcohol C and 5.5 grams (1.5%) of p-toluene sulfonic acid mono-hydrate.
  • the mixture was refluxed at 13015 0 C. for 3 hours to form a mixture of mono-ester and di-ester.
  • the amount of water collected during the reflux was 7 cc., theory 6.75 cc.
  • the ester mixture was diluted with 100 cc. of benzene.
  • To the ester mixture was added gradually at room temperature with stirring 7.5 grams (0.125 mole) of ethylenediamine and 15.25 grams (0.125 mole) of salicylaldehyde.
  • the mixture was refluxed at 102 C. for 2 hours and 150 C. for 3 hours.
  • the reaction product was diluted with 500 cc. of benzene, water-washed and.
  • Example 6 alcohol and 7.6 grams (2%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 150 C. for
  • the mixture was refluxed at 95105 C. for 3 hours and 155 C. for 2 hours.
  • the amount of water collected during the reaction was 4.5 cc., theory 4.5 cc.
  • the reaction product was water-washed and topped to 175 .C. under a pressure of 0.5 mm. of mercury.
  • Example 7 A mixture of 70 grams (0.5 mole) of 1-decene, 49
  • ester mixture was added at room temperature with stirlene.
  • To the copolymer was added at room temperature with stirring 175 grams (0.875 mole) of isotridecyl alcohol and 2.94 grams (1%) of p-toluene sulfonic acid monohydrate.
  • the mixture was gradually heated to 175 C., and held at 175 C. for 3 hours to complete the formation of a mixture of mono-ester and di-ester.
  • the amount of water collected during the esterification was 6 cc., theory 6.75 cc.
  • the ester mixture was diluted with cc. of benzene.
  • Example 8 A mixture of 84 grams (0.5 mole) of l-dodecene, 49 grams (0.5 mole) of maleic anhydride, 2.66 grams (2%) of benzoyl peroxide and 25 cc. of xylene was gradually heated with stirring. Heat was turned ofl? at 100 C. The reaction was exothermic, and the temperature rose rapidly to C., then dropped. The mixture was stirred at 150155 C. for 3 hours to complete copolymerization. The copolymer was diluted with 250 cc. of xylene.
  • T o the copolymer was added at room temperature with stirring grams (0.875 mole) of isotridecyl alcohol and 6.16 grams (2%) of p-toluene sulfonic acid monohydrate.
  • the mixture was refiuxedat 150 C. for 4 hours and 175 C. for 2 hours to form a mixture of monoester and di-ester.
  • the amount of water collected during the reflux was 7 cc., theory 6.75 cc.
  • the ester mixture was diluted with 200 cc. of benzene and water-washed To the water washed ring 15.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine.
  • the mixture was refluxed at 95 C. for 2 hours and 150-455 C. for 2 hours.
  • the amount of water collected during the reflux was 5 cc., theory 4.5 cc.
  • the reaction product was diluted with 300 cc. of benzene, water-washed and topped to 158 C. under a pressure of 1.5 mm. of mercury.
  • Example 9 Amixture of 127 grams (0.5 mole-H2 grams excess) of olefin B, 49 grams (0.5 mole) of maleic anhydride, 1.64 grams (1% of benzoyl peroxide and 5 0.cc. of xylene as diluent was stirred at 75-80 C. for 6 hours to complete copolymerization. The copolymer was diluted with 100 cc. of xylene. To the copolymer was added at room temperature with stirring 150 grams (0.75 mole) of isotridecyl alcohol and 3.14 grams (1%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 150 C. for 4 hours and 175 C.
  • Example 10 A mixture of 99 grams (0.5 mole+9 grams excess) of olefin A, 49,grams (0.5 mole) of maleic anhydride, 1.39
  • the mix- 4 about 2000 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin, having between about 2 carbon atoms and about 20 carbon atoms per molecule, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of an organic aliphatic alcohol containing between about 4 carbon atoms and about 20 carbon atoms per molecule to produce 'a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of a polyamine of the formula H N(--'R--NH) -H, wherein R is selected from the group consisting of ethylene and propylene and n varies between 1 and v2, and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product obtained by (l) csterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of butanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent al-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about l0.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and-maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of 2-ethylhexanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 molesalicylaldehyde, per mole of said ester product
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a 1-0lefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isodecanol to produce a mixed monoand di-ester product; (2) reacting said ester product between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight per cent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadccene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent 1 decen'e, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of a mixture of normal aliphatic alcohols containing about 2.8 weight percent decanol, about 61 weight percent dodecanol, about 21 weight percent tetradecanol, about 11 weight per cent hexadecanol, and about 2.2 weight percent octadecano
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of octadecenol to product amixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediarnine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said este
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of decene-l and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product obtained by (1) esterifyingea 1:1 molar copolymer of dodecene-l and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3-weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with about 1.5 moles, per
  • a liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand'barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1") esteri-fying a 1:1 molar copolymer of a l-olefin mixture, containing about 8.2 Weight percent l-hexene, about 7 weight percent l-decene, about 48 'weight percent l-dodecene, about 17.5 Weight percent,
  • a liquid hydrocarbon jet combustion fuel containing' between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition
  • an additive composition comprising the reaction product l-olefin mixture, containing about 3 weight percent 11- decene, about 66 weight percent l-dodecene, about 20 Weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent 1-octadecene,- and rnaleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand 'di-ester product; (2) reacting said ester product with betweenabout 0.25 mole and about 0.50mole of propylenediamine and between about 0.25 mole and about 0.50 mole salicyl aldehyde, per moleof said ester product;
  • a liquid hydrocarbon jet'combustio'n fuel containing between about 25 pounds per'thousand barrels of fuel and about 50 pounds per thousand barrels offuel of an additive composition comprising-the reaction product obtained by (1) esterifying a 1:1' molar copolymer of a l -olefin mixture, containing about 3 Weight percent 1- decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weightpercent jl-octadecene, and maleic acid anhydride between about 1.5 moles and about 1.75 moles, per mole of said 'copolymer, of

Description

and certain metal deactivating compounds.
Patented Aug. 28, 1962 3,553,562 STABELEZED JET CQMBEETION FUELS Paul Y. C. Gee, Flood-bury, and Harry J. Andress, 3:3, Pitman, NHL assignors to Soceny Mobil Gil Company, Inc, a corporation of New York No Drawing. Filed Jan. 24 1950, Ser. No. 3,484 13 Claims. (Cl. 44-62) This invention relates to jet combustion fuels that are stable at relatively high temperatures. It is more particularly concerned with jet combustion fuels adapted for use in high temperature jet engines and with novel additive compositions therefor.
As is well known to those familiar with the art, aviation turbine engines, or jet engines, are operated at extremely high temperatures, particularly in the case of supersonic jet aircraft engines. In order to remove some of the heat and also preheat the incoming fuel, the fuel is subjected to indirect heat exchange with the combustion chamber. Then, when passing through the injection nozzles, the incoming fuel is further subjected to high temperature conditions. Many jet fuels have been found to be relatively unstable when subjected to high temperatures. Decomposition products are formed which tend to foul the heat exchange tubes and to cause plugging of the injection nozzles. As will readily be appreciated, the use of such fuels results in shortened operational life of the engine and can be a source of hazard in the operation of the jet aircraft. Accordingly, a means of stabilizing such fuels against degradation is highly desirable.
It has now been found that thermally unstable jet combustion fuels can be stabilized against degradation simply and economically. It has been discovered that the addition of a small amount of a reaction product of certain partial esters with polyamines and a hydroxyaromatic aldehyde will stabilize jet combustion fuels against thermal degradation, thereby minimizing the fouling of heat exchange tubes and the plugging of the nozzles.
Accordingly, it is an object of this invention to pro vide stable jet combustion fuelsv Another object is to provide a means for stabilizing jet combustion fuels against thermal degradation. A further object is to provide jet combustion fuels having a greatly reduced tendency to foul heat exchange tubes and to plug injection nozzles. A specific object is to provide jet combustion fuels containing an additive composition of certain esters A more specific object is to provide jet combustion fuels containing the reaction product of certain partial esters with polyamines and hydroxyaromatic aldehyde. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.
In general, the present invention provides an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a 1-olefin, having between about 2 carbon atoms and about carbon atoms per molecule, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of a primary or secondary aliphatic alcohol containing between about 4 carbon atoms and about 20 carbon atoms per molecule to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of a polyamine of the formula H N(RNH) -H,
wherein R is ethylene or propylene and n is 1 or 2, and
between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product; and a jet combustion fuel containing between about 0.001 percent and about one percent, by weight, of the said additive composition.
The mixed monoand di-ester product used in the reaction products of this invention is the mixed mono and di-aliphatic ester of certain olefin-maleic anhydride heteropolyrners. The heteropolymer is produced by copolymerizing equimolar amounts of a l-olefin and maleie acid anhydride. The l-olefin reactant should contain between about 2 carbon atoms and about 20 carbon atoms per molecule. The reactants are heated together, either in bulk, or in the presence of a suitable solvent, such as benzene, toluene, xylene, dioxane, or carbon tetrachloride, at temperatures varying between about C. and about 175 C. Preferably, the copolymerization is carried out in the presence of a peroxide catalyst, such as benzoyl peroxide. The amount of peroxide used is between about one percent and about 5 percent, by weight of the reactants. The time required to complete the copolymerization varies between about one hour and about 10 hours.
The mixed monoand di-aliphatic ester is made by esterifying the heteropolymer with a primary or secondary aliphatic alcohol containing between about 4 carbon atoms and about '20 carbon atoms per molecule. The branched-chain alkyl alcohols are particularly preferred. Non-limiting examples of the esterifying alcohols are butanol; Z-methylpropanol; 2,2'dirnethylpropanol; amyl alcohol; isoamyl alcohol; hexanol; hexenol; 3-methyl-' pentanol; Z-ethylhexanol; isodecanol; decanol; dodecanol; iso-tridecanol; hexadecanol; hexadecenol; octadecanol; octadecenol; and eicosanol. It is to be noted that the esters utilizable herein must be a mixed monoand dialiphatic ester. acted with the olefin-maleic anhydride in amounts of between about 1.5 moles and about 1.75 moles per mole of olefin-maleic anhydride copolymer.
As will readily be appreciated by those familiar with the art the ester can be made by any of the known methods for preparing esters of carboxylic acids. For exam ple, the mixed esters of l-olefin-maleic anhydride copolymers can be prepared by heating at 200 C., from 1 to 10 hours, one mole of l-olefin-maleic anhydride copolymer with 1.5-1.75 moles of alcohol with the elimination of 0.5 0.75' mole of water. The esterification is suitably carried out in the presence of a catalyst, such as p-toluene sulfonic acid monohydrate or sulfuric acid. The amount of p-toluene sulfonic acid monohydrate or sulfuric acid used is from 0.1 percent to 5 percent by weight of the reactants. Likewise, there can be used various techniques of esterification, such as azeotropic distillation, or removal of water by the use of applied vacuum. It is to be understood that the particular method used to prepare the mixed ester component is of little importance to the additive compositions of this invention or to the jet combustion fuels containing them.
The mixed monoand di-aliphatic ester component is then further reacted with, per mole of mixed ester, between about 0.25 mole and about 0.5 mole of a polyamine reactant as hereinafter defined and between about 0.25 mole and about 0.5 mole of salicylaldehyde. The polyamine reactant has the formula H N(RNH) -H, wherein R is ethylene or propylene and n is 1 or 2. Examples of the polyamine reactant are ethylenediamine,
propylenediamine, diethylenetriamine and dipropylenetri amine. The reaction between the copolymer ester, polyamine reactant, and salicylaldehyde is a condensation reaction accompanied by the formation of water of reaction. tures varying between about 90 C. and about C. and for a period of time varying between about one hour and about 5 hours, or until water of condensation ceases to form. As was described in the case of the esterification step, various techniques of esterification (or condensation in general) are equally applicable to the reaction with amine and salicylaldehyde. Thus, for example,
Accordingly, the alcohol reactant is re- The reaction is suitably carried out at temperawater can. be removed by azeotropic distillation. Following both the esterification step and the step of reacting with amine and salicylaldehyde, it is desirableto Water- Wash. "This ensures removal of any'water-soluble matter thatinay'reniain following each step.
"Theliydrocarbon 'jet'fuelsthat are improved in accordance With this invention are hydrocarbon fractions having an initial boiling pointof at least about 100 F. and an end boiling point as high. as about 750 F. These fuels can be made up of straight-run. distillate fractions,
catalytically or thermally .cracked' (including hydrocracked) distillate fractions, or mixtures of straight-run;
fuel oil, naphtha, etc. with cracked distillate stocks, a1- kylate,'and the like. The principal. properties that'characterize the jet fuels. is their boiling range. Each fuel will have a boiling range which falls within the aforespecified'range. Specifications that define typical specific fuels a1e -MI-LF5616, MILJ -5624D, MlL-F-25656, MllF-2524A, MILF-2557.6A, MIL-P4555813, and
Theamount of additive composition, i.e. reaction product aforedescribed, that is added to the jet combustion fuels Will vary between about 0.001'percent and about onejpercent, by weight of the fuel, and preferably be-.-
. terms of weight per unit volume of fuel, the concentration of additive composition will vary between about 5.0
tween about 0.0 1'percent and about 0.02 percent.
pounds per thousand barrels of fueland about 2000 pounds per thousand barrels of fuel. Preferably, 'the concentration will vary between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousandbarrels of fuel.
The following examples are for the purpose of illustrating the additive compositions of this invention and demonstrating the effectiveness thereof in rendering jet fuels thermally stable. It must be strictly understood that the invention -is not to belimited to the particular compositions shown or to the operations or manipulations in: 'volved. A variety of other additive compositions as described. hereinbefore can be used as those skilled in the. art will readily appreciate. I
, lnthe examples, Olefin A is a "mixture containing about 8.2 Weight percent 1-heXene,'about 7 weight percent 1'-decene, about'48 weight percent l-dodecene, about 17.5 weight percent l-tetradecene, about 8.8' weight percent .l-hexadecene, and about 10.5 weight percent l-octadecene. g V e 01efin.-B- is a mixture containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about weight percent. l-tetradecene, about 10.5 Weight percent l-hexadecene, and about 0.5 weight percent l-octadecene. 7 7 Alcohol C is a mixture of normal aliphatic, mono- V hydric'alcohols containing about 2.8 weight percent decanol, about '61 weight percent dodecanol, about 21 7 weight percent tetradecanol, about 11 Weight percent 7 hxadecanol, and about 2.2 weight percent octadecanol.
7 Example 1 V 'A mixture of 115 grams (0.5 mole) of olefin B, 49' grams (0.5 mole) of maleic anhydride, 2.5 grams (1.5%)
of benzoyl peroxide and 25cc. of xylene as diluent was gradually heated with stirring. -Heat was turned off at 100 C. The reaction was exothermic, and the'temperature rose rapidly to 161 C., then dropped. The mixture was stirredat 150-155 C. for 4 hours to complete copolymeriza'tion. To the copolymer wasadded, at room temperature Withstirring, 65 grams (0.875 mole) Example 2 i V V V a mixture of 115 .grams (0.5 mole) of olefin B, 49 grams (0.5 mole) of maleic anhydride, 2.5 grams (1.5%)
of benzoyl peroxide and 25 cc..of Xylene as diluent was gradually heated with stirring.
Heat was turned off at 100 C. The reaction was exothermic, and the temperature rose rapidly to 178 C., then dropped. The mixturewas stirred'at 150 C. for 4 hours to complete copolymerization; The copolymer was diluted with 200 cc. of toluene. To the copolymer was added'at room temperature with stirring 114 grams (0.875 mole) of 2ethyl-hexyi alcohol and 5.56 grams (2%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 132 c. for 3-hours, l50 c. for 4 hours and 175 c.
for one hourto'form a mixture of mono-ester and diester. 7 The amount of water collected during the reflux was 7.5 cc.,theory 6.75 cc. The ester mixture was diluted with 150 cc. of benzene and water-washed until the water layer was neutral. To the'water-washed ester mixture was added at room temperature with-stirring 1 5.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine. The mixture was refluxed :at 95-105" C. for 2 hours and 150-165 C. for 2' hours. The amount of' water collectedduring the. reflux was 4.5 cc., theory 4.5 cc. The reaction prod- 7 not wasdiluted with 200 cc. of benzene, Water-washed and topped to 175 C. .under a pressure of 1.5 mm. of mercury- Example 3 A mixture, @115 grams (0.5 mole) of olefin B, 49
' grams (0.5h1o1e) of maleic anhydride, 2.5 grams (1.5%)
of benzoyl peroxide and 25. cc. of xylene as diluent was gradually heated withstirring. Heat was turned off at 100 C... The reaction was exothermic, and the temperature roserapidly to 178 C., then dropped. The mixture wasstirred at 150-155" C. for 4-hours to complete copolynaerization. The copolymerwas diluted with 250 cc. of xylene. To the copolymer'was added at room temperature 138 grams (0.875 mole) of isodecyl alcohol and 6.04 grams (2%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 150 C. for4 hours and 175 C. for 2 hours to form'a mixture of mono-ester and diester. The amount of water collected during the esterification was .7 cc., theory 6.75 cc. The e'stenmixture was diluted with 150 cc. of benzene and Water washed until.
' the-water layer was neutral. -To the water-Washed ester mixture was added at room temperature'withsfin'ing 15.25 grams (0.125 mole) of salicylaldehyde and'75 grams (0.125;mole). of ethylenediamine. The mixture was refluxed. at C. for 3 hours and 150-155 C. for 2 hours... The amount of water collected dUring the re- 7 action was 5 cc., theory 4.5 cc; The reaction product was c of n-butyl alcohol, 6 grams (2.6%) of p-toluene sulfonic 'acid'monohydrate. and;200 cc. of benzene. The mixture .70
Wasrefluxedat Cffor 8 hours and 150 C; for 2 amount of water collected during the esterification was 7 hours to form a mixture of mono-esterand di-ester. The
75 xylene.
diluted with 300cc. of benzene, Water-washed'and topped to: 150C. under a-pressure of 1.5 mm. of mercury.
Ewi er p A mixture 05 grams. (0.5mole) "of olefin 49 grams (0.5 mole) of maleic anhydride, 2.5 grams (115%) of benzoyl peroxideand 25 cc. of xylene as diluentwas graduallyheatedwith stirring. -Heat W'as turned off at 100 C. The reaction was exothermigand the temperature rose rapidly to 154 C.,.thndropped. The mixture V was stirred at C. for 4 hours to complete copolym- .7fcc.,.th eory 6.75 cc. The ester mixture was diluted with .200 cc of benzene'and-watenwashed until the erization. The copolymer was-diluted with 10 0- cc. of
Tothe copolymerwasadde'd at room temperature 175 grams (0.875 mole) of primary isotridecyl alcohol and 3.4 grams (1%) of p-toluene sulfonic acid monohydrate. The mixture was heated under reflux at 150 C. for 5 hours and 185 C. tor 2 hours to form a mixture of mono-ester and di-ester. The amount of water collected during the reflux was 6.75 cc., theory 6.75 cc. The ester mixture was diluted with 200 cc. of benzene. To the ester mixture was added at room temperature with stirring 15.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine. The mixture was refluxed at 90 C. for 3 hours and at 175 C. for 30 minutes. The amount of water collected during the reaction was 4.5 cc., theory 4.5 cc. The product was topped to 175C. under the house vacuum to remove the xylene.
Example 5 A mixture of 115 grams (0.5 mole) of olefin B, 49 grams (0.5 mole) of maleic anhydride, 1.65 grams (1%) of benzoyl peroxide and 30 cc. of xylene as diluent was gradually heated with stirring. Heat was turned oil at 100 C. The reaction was exothermic, and the temperature rose rapidly to 156 C., then dropped. The mixture was stirred at 150 C. for 4 hours to complete copolymerization. The copolymer was diluted with 150 cc. of toluene. To the copolymer was added at room temperature 175 grams (0.875 mole) of alcohol C and 5.5 grams (1.5%) of p-toluene sulfonic acid mono-hydrate. The mixture was refluxed at 13015 0 C. for 3 hours to form a mixture of mono-ester and di-ester. The amount of water collected during the reflux was 7 cc., theory 6.75 cc. The ester mixture was diluted with 100 cc. of benzene. To the ester mixture was added gradually at room temperature with stirring 7.5 grams (0.125 mole) of ethylenediamine and 15.25 grams (0.125 mole) of salicylaldehyde. The mixture was refluxed at 102 C. for 2 hours and 150 C. for 3 hours. The reaction product was diluted with 500 cc. of benzene, water-washed and.
topped to 160 C. under a pressure of 1.5 mm. of mercury.
Example 6 alcohol and 7.6 grams (2%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 150 C. for
3 hours and 175 C. for 2 hours to form a mixture of mono-ester and di-ester. The amount of water collected during the esterification was 7 cc.,'theory 6.75 cc. The ester mixture was diluted with 200 cc. ofbenzene and water-washed until the water layer wasneutral. To the water-washed ester mixture was added at room temperature with stirring 15.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine.
The mixture was refluxed at 95105 C. for 3 hours and 155 C. for 2 hours. The amount of water collected during the reaction was 4.5 cc., theory 4.5 cc. The reaction product was water-washed and topped to 175 .C. under a pressure of 0.5 mm. of mercury.
Example 7 A mixture of 70 grams (0.5 mole) of 1-decene, 49
grams (0.5 mole) of maleic anhydride, 1.19 grams (1%) of benzoyl peroxide and 25 cc. of xylene was gradually heated with stirring. Heat was turned ofl at 100 C. The reaction was exothermic, and the temperature rose rapidly to 152 C., then dropped. The mixture was stirred at 150 C. for 3 hours to complete copolymerization. The copolymer was diluted with 100 cc. of xyuntil the water layer was neutral.
ester mixture was added at room temperature with stirlene. To the copolymer was added at room temperature with stirring 175 grams (0.875 mole) of isotridecyl alcohol and 2.94 grams (1%) of p-toluene sulfonic acid monohydrate. The mixture was gradually heated to 175 C., and held at 175 C. for 3 hours to complete the formation of a mixture of mono-ester and di-ester. The amount of water collected during the esterification was 6 cc., theory 6.75 cc. The ester mixture was diluted with cc. of benzene. To the ester mixture was added at room temperature with stirring 15.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine. The mixture was gradually heated to C., and the temperature was held at 150 C. until water stopped coming over (about 2 hours). The amount of water collected during the reaction 'was 4.5 cc., theory 4.5 cc. The reaction product was diluted with 100 grams of xylene and was filtered through Hiflo clay.
Example 8 A mixture of 84 grams (0.5 mole) of l-dodecene, 49 grams (0.5 mole) of maleic anhydride, 2.66 grams (2%) of benzoyl peroxide and 25 cc. of xylene was gradually heated with stirring. Heat was turned ofl? at 100 C. The reaction was exothermic, and the temperature rose rapidly to C., then dropped. The mixture was stirred at 150155 C. for 3 hours to complete copolymerization. The copolymer was diluted with 250 cc. of xylene. T o the copolymer Was added at room temperature with stirring grams (0.875 mole) of isotridecyl alcohol and 6.16 grams (2%) of p-toluene sulfonic acid monohydrate. The mixture was refiuxedat 150 C. for 4 hours and 175 C. for 2 hours to form a mixture of monoester and di-ester. The amount of water collected during the reflux was 7 cc., theory 6.75 cc. The ester mixture was diluted with 200 cc. of benzene and water-washed To the water washed ring 15.25 grams (0.125 mole) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine. The mixture :was refluxed at 95 C. for 2 hours and 150-455 C. for 2 hours. The amount of water collected during the reflux was 5 cc., theory 4.5 cc. The reaction product was diluted with 300 cc. of benzene, water-washed and topped to 158 C. under a pressure of 1.5 mm. of mercury.
Example 9 Amixture of 127 grams (0.5 mole-H2 grams excess) of olefin B, 49 grams (0.5 mole) of maleic anhydride, 1.64 grams (1% of benzoyl peroxide and 5 0.cc. of xylene as diluent was stirred at 75-80 C. for 6 hours to complete copolymerization. The copolymer was diluted with 100 cc. of xylene. To the copolymer was added at room temperature with stirring 150 grams (0.75 mole) of isotridecyl alcohol and 3.14 grams (1%) of p-toluene sulfonic acid monohydrate. The mixture was refluxed at 150 C. for 4 hours and 175 C. for 2 hours to form a mixture of mono-ester and di-ester. water collected during the esterification was 4.5 cc., theory 4.5 cc. The ester mixture was diluted with 100 cc. of xylene and 150 cc. of benzene. To the ester mixture was added at room temperature with stirring 16.75 grams (0.125 mole+1.5 grams excess) of salicylaldehyde and 7.5 grams (0.125 mole) of ethylenediamine. ture was refluxed at 85-95 C. for 2 hours and 148 C. for 2 hours. The amount of water collected during the reflux was 5 cc., theory 4.5 cc. The product contained 22% xylene and was fluid at room temperature.
Example 10 A mixture of 99 grams (0.5 mole+9 grams excess) of olefin A, 49,grams (0.5 mole) of maleic anhydride, 1.39
The amount of.
The mix- 4 about 2000 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin, having between about 2 carbon atoms and about 20 carbon atoms per molecule, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of an organic aliphatic alcohol containing between about 4 carbon atoms and about 20 carbon atoms per molecule to produce 'a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of a polyamine of the formula H N(--'R--NH) -H, wherein R is selected from the group consisting of ethylene and propylene and n varies between 1 and v2, and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
2. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (l) csterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of butanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
3. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent al-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about l0.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and-maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of 2-ethylhexanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 molesalicylaldehyde, per mole of said ester product.
4. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a 1-0lefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isodecanol to produce a mixed monoand di-ester product; (2) reacting said ester product between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
5. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight per cent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadccene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
6. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent 1 decen'e, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of a mixture of normal aliphatic alcohols containing about 2.8 weight percent decanol, about 61 weight percent dodecanol, about 21 weight percent tetradecanol, about 11 weight per cent hexadecanol, and about 2.2 weight percent octadecanol to produce a mixed monoand diester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
7. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3 weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of octadecenol to product amixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediarnine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
8. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifying a 1:1 molar copolymer of decene-l and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
9. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1) esterifyingea 1:1 molar copolymer of dodecene-l and maleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand di-ester product; (2) reacting said ester product with between about 0.25 mole and about 0.50 mole of ethylenediamine and between about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
10. A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (l) esterifying a 1:1 molar copolymer of a l-olefin mixture, containing about 3-weight percent l-decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent l-octadecene, and maleic acid anhydride with about 1.5 moles, per
7 7 1 r 7 a t V i 7 mole of saidicopolymer, of isotridecanol TtO' produce a mixed 'monoand di-ester product; (2 reacting said ester product with between about 0.25 mole and about 7 0.50 mole of ethylenediamine and between about 0.25
mole and about 0.50: mole salicylaldehyde, per mole of said ester product. g V w 1.1 A liquid hydrocarbon jet combustion fuel containing between about 25 pounds per thousand'barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product obtained by (1") esteri-fying a 1:1 molar copolymer of a l-olefin mixture, containing about 8.2 Weight percent l-hexene, about 7 weight percent l-decene, about 48 'weight percent l-dodecene, about 17.5 Weight percent,
l-tetradecene, about 8.8 weight percent l-hexadecene, and about 10.5 weight percentl-octadecen e, and maleic acid lanhydlide with between about 15 moles and about 1.75
moles, per mole of said copolyrner, of isodecanol to pro:
' ducea mixed monoor di-ester product; (2) reacting said ester product'with between about 0.25 mole and about 0.50 mole of ethylenediarnine and between about-0.25
mole and about 0.50 mole salicylaldehyde, per mole of 7 said ester product.
12. A liquid hydrocarbon jet combustion fuel containing' between about 25 pounds per thousand barrels of fuel and about 50 pounds per thousand barrels of fuel of an additive composition comprising the reaction product l-olefin mixture, containing about 3 weight percent 11- decene, about 66 weight percent l-dodecene, about 20 Weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weight percent 1-octadecene,- and rnaleic acid anhydride with between about 1.5 moles and about 1.75 moles, per mole of said copolymer, of isotridecanol to produce a mixed monoand 'di-ester product; (2) reacting said ester product with betweenabout 0.25 mole and about 0.50mole of propylenediamine and between about 0.25 mole and about 0.50 mole salicyl aldehyde, per moleof said ester product;
13. A liquid hydrocarbon jet'combustio'n fuel containing between about 25 pounds per'thousand barrels of fuel and about 50 pounds per thousand barrels offuel of an additive composition comprising-the reaction product obtained by (1) esterifying a 1:1' molar copolymer of a l -olefin mixture, containing about 3 Weight percent 1- decene, about 66 weight percent l-dodecene, about 20 weight percent l-tetradecene, about 10.5 weight percent l-hexadecene, and about 0.5 weightpercent jl-octadecene, and maleic acid anhydride between about 1.5 moles and about 1.75 moles, per mole of said 'copolymer, of
'isotridecanol to produce amixed monoand di-ester product; (2) reacting said ester product with between obtained 'by (1) esterifying a121 molar copolymer of a.
about 0.25 mole and about 0.50 mole of diethylenetriamine andbetweerr about 0.25 mole and about 0.50 mole salicylaldehyde, per mole of said ester product.
References Cited in the file of this patent UNITED STATES PATENTS 2,977,334 "Zopf et a1. Mar. 28,1961

Claims (1)

1. A LIQUID HYDROCARBON JET COMBUSTION FUEL CONTAINING BETWEEN ABOUT 5 POUNDS PER THOUSAND BARRELS OF FUEL AND ABOUT 2000 POUNDS PER THOUSAND BARRELS OF FUEL OF AN ADDITIVE COMPOSITION COMPRISING THE REACTION PRODUCT OBTAINED BY (1) ESTERIFYING A 1:1 MOLAR COPOLYMER OF A 1-OLEFIN, HAVING BETWEEN ABOUT 2 CARBON ATOMS AND ABOUT 20 CARBON ATOMS PER MOLECULE, AND MALEIC ACID ANHYDRIDE WITH BETWEEN ABOUT 1:5 MOLES AND ABOUT 1.75 MOLES, PER MOLE OF SAID COPOLYMER, OF AN ORGANIC ALIPHATIC ALCOHOL CONTAINING BETWEEN ABOUT 4 CARBON ATOMS AND ABOUT 20 CARBON ATOMS PER MOLECULE TO PRODUCE A MIXED MONOAND DI-ESTER PRODUCT; (2) REACTING SAID ESTER PRODUCT WITH BETWEEN ABOUT 0.25 MOLE AND ABOUT 0.50 MOLE OF A POLYAMINE OF THE FORMULA H2N(-R-NH)N-H, WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF ETHYLENE AND PROPLYENE AND N VARIES BETWEEN 1 AND 2, AND BETWEEN ABOUT 0.25 MOLE AND ABOUT 0.50 MOLE SALICYLALDEHYDE, PER MOLE OF SAID ESTER PRODUCT.
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US3236613A (en) * 1962-03-20 1966-02-22 Socony Mobil Oil Co Inc Petroleum distillates containing reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde
US3336384A (en) * 1962-03-20 1967-08-15 Mobil Oil Corp Reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde
US3458295A (en) * 1965-10-12 1969-07-29 Chevron Res Corrosion inhibitors
US3459518A (en) * 1966-12-22 1969-08-05 Chevron Res Sulfonyl substituted terpolymer fuel detergents
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US4859752A (en) * 1987-09-11 1989-08-22 S. C. Johnson & Son, Inc. Alkene/excess maleic anhydride polymer manufacture
US4959077A (en) * 1987-09-15 1990-09-25 Basf Aktiengesellschaft Fuels for gasoline engines
US5069684A (en) * 1989-12-18 1991-12-03 Mobil Oil Corporation Fuel and lube additives from polyether derivatives of polyamine alkenyl succinimides
US5770656A (en) * 1995-09-22 1998-06-23 E.I. Du Pont De Nemours And Company Partial fluoroesters or thioesters of maleic acid polymers and their use as soil and stain resists
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236613A (en) * 1962-03-20 1966-02-22 Socony Mobil Oil Co Inc Petroleum distillates containing reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde
US3336384A (en) * 1962-03-20 1967-08-15 Mobil Oil Corp Reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde
US3458295A (en) * 1965-10-12 1969-07-29 Chevron Res Corrosion inhibitors
US3459518A (en) * 1966-12-22 1969-08-05 Chevron Res Sulfonyl substituted terpolymer fuel detergents
US4151069A (en) * 1974-10-17 1979-04-24 Exxon Research & Engineering Co. Olefin-dicarboxylic anhydride copolymers and esters thereof are dewaxing aids
US4090946A (en) * 1975-07-12 1978-05-23 Basf Aktiengesellschaft Method of stabilizing mineral oil and its refinery products
US4192930A (en) * 1977-06-16 1980-03-11 Akzona Incorporated Esterified olefin-maleic anhydride copolymers
EP0306992A2 (en) 1987-09-11 1989-03-15 S.C. Johnson & Son, Inc. 1-alkene/excess maleic anhydride polymers
US4859752A (en) * 1987-09-11 1989-08-22 S. C. Johnson & Son, Inc. Alkene/excess maleic anhydride polymer manufacture
US4959077A (en) * 1987-09-15 1990-09-25 Basf Aktiengesellschaft Fuels for gasoline engines
US5069684A (en) * 1989-12-18 1991-12-03 Mobil Oil Corporation Fuel and lube additives from polyether derivatives of polyamine alkenyl succinimides
US5770656A (en) * 1995-09-22 1998-06-23 E.I. Du Pont De Nemours And Company Partial fluoroesters or thioesters of maleic acid polymers and their use as soil and stain resists
US20130059983A1 (en) * 2010-05-28 2013-03-07 Air Water Inc. Method of manufacturing esterified substance
US9070628B2 (en) * 2010-05-28 2015-06-30 Sumitomo Bakelite Co., Ltd. Method of manufacturing esterified substance

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