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EP0385633A1 - Middle distillate fuel having improved storage stability - Google Patents

Middle distillate fuel having improved storage stability Download PDF

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Publication number
EP0385633A1
EP0385633A1 EP90301791A EP90301791A EP0385633A1 EP 0385633 A1 EP0385633 A1 EP 0385633A1 EP 90301791 A EP90301791 A EP 90301791A EP 90301791 A EP90301791 A EP 90301791A EP 0385633 A1 EP0385633 A1 EP 0385633A1
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EP
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Prior art keywords
alkyl
formula
butyl
phenol
fuel
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Granted
Application number
EP90301791A
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German (de)
French (fr)
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EP0385633B1 (en
Inventor
John Gray Bostick
Larry John Cunningham
John Vincent Hanlon
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Afton Chemical Corp
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Afton Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/221Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/232Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/228Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2493Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds

Definitions

  • This invention relates generally to improving the stability of middle distillate fuels and more particularly to stabilized middle distillate fuel compositions which contain a combination of N,N-dimethylcyclohexyl amine and a Mannich Base.
  • Patent 3,490,882 discloses stabilized petroleum distillate fuel oils containing N,N-dimethylcyclohexylamine antioxidant and a N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine metal deactivator such as N,N′-disalicylidene-1,2-­propylenediamine;
  • U.S. Patent 4,166,726 discloses a fuel additive which is a mixture of a polyalkylene amine and a Mannich Base; and U.S.
  • Patents 4,501,595 and 4,533,361 disclose diesel oil which contains a condensate of tetra­ethylene pentamine, paraformaldehyde, a hindered phenol such as 2,6-di-t-butylphenol and polyisobutenyl succinic anhydride.
  • a fuel additive concentrate comprising a mixture of N,N-dimethylcyclohexylamine and a Mannich Base which is the reaction product of an aldehyde, an amine and an alkyl phenol selected from (a) hindered phenol having the formula: where R1, R2, R3 are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided that at least one of R1, R2 and R3 is hydrogen and at least one of R1 and R2 is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula: where R4 is C9 to C30 alkyl.
  • the concentrate can also contain a N,N′-di(ortho-hydroxy­arylidene)-1,2-alkylenediamine metal deactivator such as N,N′-disalicylidene-1,2-propylenediamine.
  • a stabilized fuel containing from 1 to 1400 mgs/liter of N,N-dimethylcyclohexylamine, from 0.5 to 1100 mgs/liter of Mannich Base and from 0 to 400 mgs/liter of an N,N′-­di(ortho-hydroxyarylidene)-1,2-alkylenediamine.
  • the N,N-dimethylcyclohexylamine component of the compositions of the invention is a commercially available fuel antioxidant.
  • the N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenedi­amine component in which, typically, the arylidene radi­cal contains 6-7 carbon atoms and the alkylene radical contains 2-3 carbon atoms, is a metal deactivator whose presence in combination with the other components provides fuel compositions of the invention having the most im­proved stability.
  • the preferred metal deactivator is N,N′-disalicylidene-1,2-propylenediamine which is com­mercially available.
  • the Mannich Base component of the invention is pro­duced by the Mannich condensation reaction of a hindered or p-alkyl phenol, an aldehyde, such as formaldehyde, ethanal, propanal, and butanal (preferably formaldehyde in its monomeric form or paraformaldehyde) and primary and secondary amines.
  • a hindered or p-alkyl phenol such as formaldehyde, ethanal, propanal, and butanal (preferably formaldehyde in its monomeric form or paraformaldehyde) and primary and secondary amines.
  • the hindered phenols which are useful in preparing the Mannich Base component of the invention are phenols which are characterized by the presence of at least one and preferably two ortho-t-butyl, t-amyl, and/or isopropyl groups. Specific examples of such hindered phenols in­clude: 2,4-di-t-butylphenol, 2,4-diisopropylphenol, 2,6-­diisopropylphenol, 2-t-butylphenol, and 2-t-amylphenol with 2,6-di-t-butylphenol being most preferred.
  • the p-alkyl phenols which are useful in preparing the Mannich Base component of the invention are those which contain from 9 to 30 carbons which can be arranged in either a straight or a branched chain.
  • Preferred phenols are C9 to C12 p-alkylphenols such as, for example, p-nonylphenol and p-dodecylphenol.
  • the amines which are useful in preparing the Mannich Base component of the invention are primary and secondary amines which can be selected from one or more of:
  • amines include 1,3-di­aminopropane, 1,2 diaminopropane, dimethylamine, diethyl­amine, dipropylamine, dibutylamine, N,N-dimethyl-1,3-­diaminopropane, 1,1-dimethyldodecylamine, mixed C12-­C14 t-alkyl amines, 2-methyl-1,5-pentadiamine, ethylenediamine; cyclic amines such as piperazine, aminoethylpiperazine, morpholine and thiomorpholine; and ethylene polyamines such as diethylene triamine and triethylene tetraamine.
  • the Mannich Base can be formed by reacting from 1 to 5 moles of aldehyde, from about 1 to 2 moles of amine and from 1 to 4 moles of phenol at a temperature of from 0°C to 150°C for 0.5 to 10 hours.
  • An inert solvent such as isopropanol can be used which is distilled from the product along with water formed in the reaction.
  • the Mannich Base product is usually a mixture of materials which may contain unreacted ingredients, especially the phenol.
  • the Mannich Bases can be isolated from the product mixture but the product mixture itself can conveniently be used in forming the compositions of the invention. Examples of Mannich reactions and products are illustrated below: where R1, R2, R4, R5 and R6 are as defined above.
  • additive mixtures of the invention are usually prepared and marketed in the form of concentrates for addition to the fuel by the customer although the in­dividual components could be added directly into the fuel.
  • Suitable proportions of additives in the concen­trates of the invention, based on the total weight of concentrate, include from 25 to 95 wt% N,N-dimethylcyclo­hexylamine, from 0 to 25 wt% N,N′-di(ortho-hydroxyaryli­dene)-1,2-alkylenediamine and, from 5 to 75 wt% Mannich Base.
  • the concentrates are added to the fuel in effective amounts to provide improved stability.
  • Suitable amounts of additive concentrate in the fuel are from 1 to 500 pounds per thousand barrels (Ptbs) (3 to 1500 mgs/liter, preferred 2.5 to 100 Ptbs or 8 to 300 mgs/liter).
  • Ptbs pounds per thousand barrels
  • This will provide a stabilized fuel containing from 1 to 1400 mgs/liter (preferred 2 to 250 mgs/liter) N,N-dimethylcyclo­hexylamine, from 0 to 400 mgs/liter (preferred 0 to 100 mgs/liter) N,N′-di(ortho-hydroxyarylidene)-1,2-alkylene­diamine metal deactivator and from 1 to 1100 mgs/liter (preferred 1 to 250 mgs/liter) of Mannich Base.
  • the metal deactivator When used, the metal deactivator is present in amounts of 1.0% to 25 wt% of concentrate or .3 to 400 mgs/liter of fuel.
  • the concentrates can also contain an inert diluent or solvent which can be, for example, an aliphatic hydro­carbon such as kerosene or an aromatic hydrocarbon such as xylene.
  • the middle distillate fuels whose stability is improved by the invention typically include those boiling within a temperature range of 150°-400°C which may commonly be labeled as kerosene, fuel oil, diesel oil, No. 1-D, or No. 2-D.
  • compositions of the invention are further illustrated by, but are not intended to be limited to, the following examples wherein parts are parts by weight unless otherwise indicated.
  • a Mannich Base reaction product of formaldehyde, 1,3-diaminopropane and 2,6-di-t-butylphenol is prepared by the following process.
  • Additive blends of the reaction product were prepared and tested in different fuels using both the D 4625 43°C (110°F) Storage Stability Test, in which the color change (using ASTM D1500) and the total insolubles in the fuel (reported in mg/100 ml) are determined on 400 ml samples stored for 13 weeks in the dark and the F-21-61 149°C (300°F) Accelerated Stability Test in which the color change and insoluble gums are determined on 50 ml samples heated to 149°C for a selected time, which was 90 minutes, allowed to cool in the dark, tested for color (ASTM D1500), and then filtered (using a 4.25 cm Whatman #1 filter paper) and the filtrate discarded.
  • D 4625 43°C (110°F) Storage Stability Test in which the color change (using ASTM D1500) and the total insolubles in the fuel (reported in mg/100 ml) are determined on 400 ml samples stored for 13 weeks in the dark and the F-21-61 149
  • a significant difference in stability at 149°C is indicated by a color difference of about 1/2 number and/or a deposit difference of 2 numbers and a significant dif­ference in stability at 43°C is indicated by a color dif­ference of about 1/2 number and a deposit difference of 20%.
  • the results in Table I show that the blends of the invention which contain Mannich Base in addition to DMCA or DMCA and MDA gave significantly better overall stabil­ity when compared to comparable blends which did not con­tain the Mannich Base, for example, blend 3 vs blend 2 and blend 5 vs blend 4 of Fuel #1.
  • a Mannich Base reaction product of formaldehyde, dimethylamine, and 2,6-di-t-butylphenol is prepared by the following process.
  • a Mannich Base reaction product of formaldehyde, C12-C14 t-alkyl amine mixture (Primene 81R) and 2,6-­di-t-butyl phenol is prepared by the process described in Example 2 using 95.5 grams (0.5 mole) of Primene 81R in place of the dimethylamine.
  • the product yield is 200 grams or 82% of theory which contains N-[3,5-di-t-butyl-4-­hydroxybenzyl]-mixed C12-C14 t-alkyl amines.
  • blends 4 and 7 according to the invention which contain the Mannich Base in addi­tion to DMCA and MDA have better stability at the same total additive levels compared to blends 2 and 5 contain­ing only DMCA and MDA.
  • a Mannich Base reaction product of formaldehyde, 1,2-diaminopropane, and 2,6-di-t-butyl phenol is prepared by the following process.
  • Blend 4 of the invention containing the Mannich Base has improved stability com­pound to blend 2 which containing DMCA alone.
  • Blend 5 containing the Mannich Base has improved stability over blend 3 which contained DMCA and MDA alone.
  • a Mannich Base reaction product of formaldehyde, N,N-dimethyl-1,3-diaminopropane, and p-dodecylphenol was prepared by the following procedure.

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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)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Stabilized middle distillate fuels and stabilizer additives include N,N-dimethylcyclohexylamine, a metal deactivator and a Mannich Base derived from a hindered or p-alkylphenol, formaldehyde and an amine.

Description

  • This invention relates generally to improving the stability of middle distillate fuels and more particularly to stabilized middle distillate fuel compositions which contain a combination of N,N-dimethylcyclohexyl amine and a Mannich Base.
  • Middle distillate fuels such as diesel oil, fuel oil, jet fuel and kerosene when stored for long periods of time are subject to the formation of color and solid depos­its. The deposits accumulate on filters causing the fil­ters to become plugged. Various additives and combina­tions of additives have been employed to reduce color and deposit formation. For example: U.S. Patent 2,984,550 discloses the use of Mannich bases derived from phenols, formaldehyde and polyamines for stabilization; U.S. Patent 3,490,882 discloses stabilized petroleum distillate fuel oils containing N,N-dimethylcyclohexylamine antioxidant and a N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine metal deactivator such as N,N′-disalicylidene-1,2-­propylenediamine; U.S. Patent 4,166,726 discloses a fuel additive which is a mixture of a polyalkylene amine and a Mannich Base; and U.S. Patents 4,501,595 and 4,533,361 disclose diesel oil which contains a condensate of tetra­ethylene pentamine, paraformaldehyde, a hindered phenol such as 2,6-di-t-butylphenol and polyisobutenyl succinic anhydride.
  • The effectiveness of any particular type of addi­tive combination can vary with different fuel stocks and combinations which are more effective at the same total additive concentration reduce treatment cost. We have now discovered novel, synergistic additive combinations which include certain Mannich Bases and provide middle distill­ate fuels having generally improved storage stability compared to fuels containing the same total concentrations of either N,N-dimethylcyclohexylamine antioxidant alone or N,N-dimethylcyclohexylamine in combination with an N,N′-di­(ortho-hydroxyarylidene)-1,2-alkylenediamine metal deacti­vator.
  • In accordance with this invention, there is pro­vided a fuel additive concentrate comprising a mixture of N,N-dimethylcyclohexylamine and a Mannich Base which is the reaction product of an aldehyde, an amine and an alkyl phenol selected from (a) hindered phenol having the formula:
    Figure imgb0001
    where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
    Figure imgb0002
    where R₄ is C₉ to C₃₀ alkyl.
    The concentrate can also contain a N,N′-di(ortho-hydroxy­arylidene)-1,2-alkylenediamine metal deactivator such as N,N′-disalicylidene-1,2-propylenediamine. Also provided is a stabilized fuel containing from 1 to 1400 mgs/liter of N,N-dimethylcyclohexylamine, from 0.5 to 1100 mgs/liter of Mannich Base and from 0 to 400 mgs/liter of an N,N′-­di(ortho-hydroxyarylidene)-1,2-alkylenediamine.
  • The N,N-dimethylcyclohexylamine component of the compositions of the invention is a commercially available fuel antioxidant.
  • The N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenedi­amine component, in which, typically, the arylidene radi­cal contains 6-7 carbon atoms and the alkylene radical contains 2-3 carbon atoms, is a metal deactivator whose presence in combination with the other components provides fuel compositions of the invention having the most im­proved stability. The preferred metal deactivator is N,N′-disalicylidene-1,2-propylenediamine which is com­mercially available.
  • The Mannich Base component of the invention is pro­duced by the Mannich condensation reaction of a hindered or p-alkyl phenol, an aldehyde, such as formaldehyde, ethanal, propanal, and butanal (preferably formaldehyde in its monomeric form or paraformaldehyde) and primary and secondary amines.
  • The hindered phenols which are useful in preparing the Mannich Base component of the invention are phenols which are characterized by the presence of at least one and preferably two ortho-t-butyl, t-amyl, and/or isopropyl groups. Specific examples of such hindered phenols in­clude: 2,4-di-t-butylphenol, 2,4-diisopropylphenol, 2,6-­diisopropylphenol, 2-t-butylphenol, and 2-t-amylphenol with 2,6-di-t-butylphenol being most preferred.
  • The p-alkyl phenols which are useful in preparing the Mannich Base component of the invention are those which contain from 9 to 30 carbons which can be arranged in either a straight or a branched chain. Preferred phenols are C₉ to C₁₂ p-alkylphenols such as, for example, p-nonylphenol and p-dodecylphenol.
  • The amines which are useful in preparing the Mannich Base component of the invention are primary and secondary amines which can be selected from one or more of:
    • A. alkyl monoamines of the formula;
      Figure imgb0003
      where R₅ is selected from H and C₁ to C₅ alkyl, and R₆ is selected from C₁ to C₁₄ alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
    • B. alkyl diamines of the formula;
      Figure imgb0004
      where R₅ is selected from H and C₁ to C₅ alkyl, R₈ is C₁ to C₆ alkylene and A and B are in­dependently selected from H, C₁ to C₅ alkyl, mono­hydroxysubstituted C₁ to C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
    • C. ethylene polyamines of the formula;
      H₂N(̵(CH₂)₂NH)̵nH
      where n = 2 to 10, and
    • D. cyclic amines of the formula;
      Figure imgb0005
      where n and m are independently integers from 1 to 3, X is selected from CH₂, O, S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10. The alkyl groups can have a branched chain.
  • Specific examples of such amines include 1,3-di­aminopropane, 1,2 diaminopropane, dimethylamine, diethyl­amine, dipropylamine, dibutylamine, N,N-dimethyl-1,3-­diaminopropane, 1,1-dimethyldodecylamine, mixed C₁₂-­C₁₄ t-alkyl amines, 2-methyl-1,5-pentadiamine, ethylenediamine; cyclic amines such as piperazine, aminoethylpiperazine, morpholine and thiomorpholine; and ethylene polyamines such as diethylene triamine and triethylene tetraamine.
  • The Mannich Base can be formed by reacting from 1 to 5 moles of aldehyde, from about 1 to 2 moles of amine and from 1 to 4 moles of phenol at a temperature of from 0°C to 150°C for 0.5 to 10 hours. An inert solvent such as isopropanol can be used which is distilled from the product along with water formed in the reaction.
  • The Mannich Base product is usually a mixture of materials which may contain unreacted ingredients, especially the phenol. The Mannich Bases can be isolated from the product mixture but the product mixture itself can conveniently be used in forming the compositions of the invention. Examples of Mannich reactions and products are illustrated below:
    Figure imgb0006
    where R₁, R₂, R₄, R₅ and R₆ are as defined above.
  • The additive mixtures of the invention are usually prepared and marketed in the form of concentrates for addition to the fuel by the customer although the in­dividual components could be added directly into the fuel. Suitable proportions of additives in the concen­trates of the invention, based on the total weight of concentrate, include from 25 to 95 wt% N,N-dimethylcyclo­hexylamine, from 0 to 25 wt% N,N′-di(ortho-hydroxyaryli­dene)-1,2-alkylenediamine and, from 5 to 75 wt% Mannich Base.
  • The concentrates are added to the fuel in effective amounts to provide improved stability. Suitable amounts of additive concentrate in the fuel are from 1 to 500 pounds per thousand barrels (Ptbs) (3 to 1500 mgs/liter, preferred 2.5 to 100 Ptbs or 8 to 300 mgs/liter). This will provide a stabilized fuel containing from 1 to 1400 mgs/liter (preferred 2 to 250 mgs/liter) N,N-dimethylcyclo­hexylamine, from 0 to 400 mgs/liter (preferred 0 to 100 mgs/liter) N,N′-di(ortho-hydroxyarylidene)-1,2-alkylene­diamine metal deactivator and from 1 to 1100 mgs/liter (preferred 1 to 250 mgs/liter) of Mannich Base. When used, the metal deactivator is present in amounts of 1.0% to 25 wt% of concentrate or .3 to 400 mgs/liter of fuel. The concentrates can also contain an inert diluent or solvent which can be, for example, an aliphatic hydro­carbon such as kerosene or an aromatic hydrocarbon such as xylene.
  • The middle distillate fuels whose stability is improved by the invention typically include those boiling within a temperature range of 150°-400°C which may commonly be labeled as kerosene, fuel oil, diesel oil, No. 1-D, or No. 2-D.
  • The compositions of the invention are further illustrated by, but are not intended to be limited to, the following examples wherein parts are parts by weight unless otherwise indicated.
  • Example 1
  • A Mannich Base reaction product of formaldehyde, 1,3-diaminopropane and 2,6-di-t-butylphenol is prepared by the following process.
  • Dissolve 103 grams (0.5 mole) of 2,6-di-t-butyl­phenol in 100 grams of isopropyl alcohol (IPA) in a 500 ml round bottom flask. Add 18.5 grams (0.25 mole) of 1,3-di­aminopropane dropwise over 15 minutes while the contents of the flask are stirred. There is an exotherm observed as the amine is added. Cool the contents of the flask to below 30°C and add a 10% excess, (44.6 grams 0.55 mole) of 37% aqueous formaldehyde solution dropwise over 30 minutes while maintaining the temperature below 30°C. Heat the contents of the flask to reflux and continue to reflux for one hour. Switch from reflux to distillation and distill off IPA/water mixture to 105°C. Apply 28 in. Hg vacuum to remove residual materials. The total product yield is 122.2 or 96% of theory which contains compounds of the Structure III and IV.
  • Additive blends of the reaction product were prepared and tested in different fuels using both the D 4625 43°C (110°F) Storage Stability Test, in which the color change (using ASTM D1500) and the total insolubles in the fuel (reported in mg/100 ml) are determined on 400 ml samples stored for 13 weeks in the dark and the F-21-61 149°C (300°F) Accelerated Stability Test in which the color change and insoluble gums are determined on 50 ml samples heated to 149°C for a selected time, which was 90 minutes, allowed to cool in the dark, tested for color (ASTM D1500), and then filtered (using a 4.25 cm Whatman #1 filter paper) and the filtrate discarded. The filter is washed clean of fuel with isooctane and measured for deposits by comparison with a set of reference papers. The blend compositions and test results in comparison to untreated fuel and blends without the Mannich Base product are reported in Table I below. TABLE I
    Composition in Pounds Per Thousand Barrels
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    DMCA¹ 0.0 5.0 4.0 4.75 3.80 0.0 4.75 3.8 0.0 9.5 7.6 0.0 2.38 1.90 4.75 3.80
    MDA² 0.0 0.0 0.0 0.25 0.25 0.0 0.25 0.24 0.0 0.5 0.5 0.0 0.12 0.12 0.25 0.24
    Mannich Base 0.0 0.0 1.0 0.00 0.95 0.0 0.0 0.96 0.0 0.0 1.9 0.0 0.00 0.48 0.00 0.96
    Total Additives 0.0 5.0 5.0 5.0 5.0 0.0 5.0 5.0 0.0 10.0 10.0 0.0 2.5 2.5 5.0 5.0
    Test Results
    149°C (F-21-61)
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    Color L7 L3.5 2.5 L3 2 8 3 3 8 L2.5 2 L2.5 2 2 2.5 L2.5
    Deposit 13 5 4 4 2 17 10 5 17 5 3 6 4 4 4 4
    43°C (D 4625)
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    Color L5 4 4 4 L4 L3.5 L3.5 L3.5 L3.5 L3.5 L3.5 2.5 L2.5 L2.5 L2.5 L2.5
    Deposit 6.8 3.2 2.4 2.5 1.8 7.9 4 4.7 6.7 3 2.1 2.2 2 1.6 1.3 1
    L = less than
    ¹N,N-dimethylcyclohexylamine
    ²N,N′-disalicylidene-1,2-propylenediamine
    Fuel #1 is Midwest Refinery
    Fuel #2 is Mid-Continent #2 Diesel (Corning Crude)
    Fuel #3 is Mid-Continent #2 Diesel (Ill. Basin Crude)
    Fuel #4 is Midwest #2 Diesel (KS/Tx Crude)
  • A significant difference in stability at 149°C is indicated by a color difference of about 1/2 number and/or a deposit difference of 2 numbers and a significant dif­ference in stability at 43°C is indicated by a color dif­ference of about 1/2 number and a deposit difference of 20%. The results in Table I show that the blends of the invention which contain Mannich Base in addition to DMCA or DMCA and MDA gave significantly better overall stabil­ity when compared to comparable blends which did not con­tain the Mannich Base, for example, blend 3 vs blend 2 and blend 5 vs blend 4 of Fuel #1.
  • Example 2
  • A Mannich Base reaction product of formaldehyde, dimethylamine, and 2,6-di-t-butylphenol is prepared by the following process.
  • Dissolve 103 grams (0.5 mole) of 2,6-di-t-butyl­phenol in 100 grams of IPA in a 500 ml round bottom flask and add 72 grams (0.64 mole) of a 40% aqueous dimethyl­amine solution. Cool the mixture to about 30°C and add dropwise with stirring 44.6 grams (0.55 mole) of 37% formaldehyde while keeping the mixture at a temperature below 40°C. Heat the mixture to reflux and reflux for 4 hours. Remove IPA/water by distillation and apply vacuum to remove residual materials. The product yield is 113 grams or 86% of theory which contains N,N-dimethyl-3,5-di-­t-butyl4-hydroxybenzylamine.
  • Additive blends of the above reaction product were prepared and tested in different fuels using the test procedures described in Example 1. The blend compositions and test results in comparison to untreated fuel and blends which did not contain the Mannich Base product are reported in Table II below. TABLE II
    Composition in Pounds Per Thousand Barrels
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    DMCA 0.0 5.0 4.0 4.75 3.80 0.0 9.5 7.6 0.0 28.5 22.8 0.0 2.38 1.90 4.75 3.80
    MDA 0.0 0.0 0.0 0.25 0.25 0.0 0.5 0.5 0.0 1.5 1.5 0.0 0.12 0.12 0.25 0.24
    Mannich Base 0.0 0.0 1.0 0.00 0.95 0.0 0.0 1.9 0.0 0.0 5.7 0.0 0.00 0.48 0.00 0.96
    Total Additives 0.0 5.0 5.0 5.0 5.0 0.0 10.0 10.0 0.0 30.0 30.0 0.0 2.5 2.5 5.0 5.0
    Test Results
    149°C (F-21-61)
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    Color L7 L3.5 3 L3 L3 8 3 3 4.5 L4 3.5 L2.5 2 L2.5 2.5 L2.5
    Deposit 13 5 6 4 4 17 10 6 5 3 3 6 4 5 4 3
    43°C (D 4625)
    Fuel #1 Fuel #2 Fuel #3 Fuel #4
    Components 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 5
    Color L5 4 4 4 4 L3.5 L3.5 L3.5 -- -- -- 2.5 L2.5 L3 L2.5 L2.5
    Deposit 6.8 3.2 2.8 2.5 2 6.7 4 3.9 -- -- -- 2.2 2 1.9 1.3 0.9
    The fuels were the same as in Example 1 except that Fuel #3 is a fuel containing unhydrotreated residual cracked stock.
  • The results indicated that the blends containing Mannich Base gave fuels having significantly improved stability except in the case of Fuel #4 where the results were mixed.
  • Example 3
  • A Mannich Base reaction product of formaldehyde, C₁₂-C₁₄ t-alkyl amine mixture (Primene 81R) and 2,6-­di-t-butyl phenol is prepared by the process described in Example 2 using 95.5 grams (0.5 mole) of Primene 81R in place of the dimethylamine. The product yield is 200 grams or 82% of theory which contains N-[3,5-di-t-butyl-4-­hydroxybenzyl]-mixed C₁₂-C₁₄ t-alkyl amines.
  • Additive blends of the above reaction product were prepared and tested in #2 diesel fuel using the test procedures described in Example 1. The blend compositions and test results are reported in Table III below. TABLE III
    Composition Pounds Per Thousand Barrels
    Components 1 2 3 4 5 6 7
    DMCA 0.0 9.5 0.0 4.75 19.0 0.0 9.5
    MDA 0.0 0.5 0.5 0.50 1.0 1.0 1.0
    Mannich Base 0.0 0.0 9.5 4.75 0.0 19.0 9.5
    Total Additives 0.0 10.0 10.0 10.0 20.0 20.0 20.0
    Test Results
    149°C (F-21-61)
    Components 1 2 3 4 5 6 7
    Color L5.5 L4.5 L5 L4.5 L4.5 L5 L4.5
    Deposit 8 6 4 3 4 3 2
    43°C (D 4625)
    Components 1 2 3 4 5 6 7
    Color L6.5 L6 6 L6 5.5 L6 L5.5
    Deposit 8.3 3.2 5 2.8 3.3 5 3
  • The results indicate that blends 4 and 7 according to the invention which contain the Mannich Base in addi­tion to DMCA and MDA have better stability at the same total additive levels compared to blends 2 and 5 contain­ing only DMCA and MDA.
  • Example 4
  • A Mannich Base reaction product of formaldehyde, 1,2-diaminopropane, and 2,6-di-t-butyl phenol is prepared by the following process.
  • Dissolve 103 gm (0.5 mole) of 2,6-di-t-butyl phenol in 100 grams of IPA in a 500 ml roundbottom flask and add 18.5 grams (0.25) moles of 1,2-diaminopropane. Cool this mixture to about 30°C and add dropwise with stirring 44.6 grams (0.55 mole) of 37% formaldehyde while keeping the temperature of the mixture below 40°C. Heat the mixture to reflux and reflux for 1 hour. Remove IPA/water by distillation and apply vacuum to remove residual materi­als.
  • Additive blends of the above reaction product were prepared and tested in Fuel #1 fuel using the test proce­dures described in Example 1. The blend compositions and results are reported in Table IV below. TABLE IV
    Composition Pounds Per Thousand Barrels
    Components 1 2 3 4 5
    DMCA 0.0 5.0 4.75 4.0 3.8
    MDA 0.0 0.0 0.25 0.0 0.25
    Mannich Base 0.0 0.0 0.00 1.0 0.95
    Total Additives 0.0 5.0 5.0 5.0 5.0
    Test Results
    149°C (F-21-61)
    Components 1 2 3 4 5
    Color L7 L3.5 L3 L3 L2.5
    Deposit 13 5 4 3 3
    43°C (D 4625)
    Components 1 2 3 4 5
    Color L5 4 4 4 L4
    Deposit 6.8 3.2 2.5 2.6 1.7
  • The results indicate that blend 4 of the invention containing the Mannich Base has improved stability com­pound to blend 2 which containing DMCA alone. Blend 5 containing the Mannich Base has improved stability over blend 3 which contained DMCA and MDA alone.
  • Example 5
  • A Mannich Base reaction product of formaldehyde, N,N-dimethyl-1,3-diaminopropane, and p-dodecylphenol was prepared by the following procedure.
  • Combine 262.4 grams (1.0 mole) of the alkyl (C₁₂) phenol with 102.2 grams (1.0 mole) of N,N-dimethyl-1,3-di­amino-propane and add 89.2 grams (1.1 mole) of 37% formal­dehyde with stirring while keeping the temperature below 40°C. Heat the mixture to 100°C for two hours and then remove water by distillation (100°C - 28 in vacuum). The product yield is 176 grams or 93% of theory which contains N,N-dimethyl-N′-[2 hydroxy-5-dodecylbenzyl]-1,3-diamino­propane.
  • Additive blends of the above reaction product were prepared and tested in midcontinent #2 diesel fuel using the test procedures described in Example 1. The blend compositions and results are reported on Table V below. TABLE V
    Composition Pounds Per Thousand Barrels
    Components 1 2 3 4 5
    DMCA 0.0 4.75 2.05 9.5 4.5
    MDA 0.0 0.25 0.25 0.5 0.5
    Mannich Base 0.0 0.00 2.70 0.0 5.4
    Total Additives 0.0 5.0 5.0 10.0 10.0
    Test Results
    149°C (F-21-61)
    Components 1 2 3 4 5
    Color 8 3 L3 L2.5 L2.5
    Deposit 13 10 5 5 5
    43°C (D 4625)
    Components 1 2 3 4 5
    Color L3.5 L3.5 3 L3.5 L3.5
    Deposit 6 4 3.5 3 2.4
  • The results indicate that blends 3 and 5 of the in­vention have over-all improved stability compared to blends at the same total additive level which did not in­clude the Mannich Base.

Claims (10)

1. A fuel additive concentrate comprising a mix­ture of N,N-dimethylcyclohexylamine and a Mannich Base which is the reaction product of an aldehyde, a primary or secondary amine and an alkyl phenol selected from (a) hindered phenol having the formula:
Figure imgb0007
where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
Figure imgb0008
where R₄ is C₉ to C₃₀ alkyl; said concentrate containing, based on the total weight of concentrate, from 25 to 95 wt% N,N-dimethylcyclohexylamine from 5 to 75 wt% Mannich Base.
2. The concentrate of claim 1 wherein the concen­trate also contains from 1 to 25 wt% N,N′-di(ortho-hydroxy­arylidene)-1,2-alkylenediamine metal deactivator.
3. The concentrate of claim 1 or 2 wherein the aldehyde is formaldehyde, and the amine is selected from one or more of:
A. alkyl monoamines of the formula;
Figure imgb0009
where R₅ is selected from H and C₁ to C₅ alkyl, and R₆ is selected from C₁ to C₁₄ alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
B. alkyl diamines of the formula;
Figure imgb0010
where R₅ is selected from H and C₁ to C₅ alkyl, R₈ is C₁ to C₆ alkylene and A and B are independently selected from H, C₁ to C₅ alkyl, mono-hydroxysubstituted C₁ to C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
D. cyclic amines of the formula;
Figure imgb0011
where n and m are independently intergers from 1 to 3, X is selected from CH₂, 0, S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10.
4. The concentrate of any of the preceding claims wherein the phenol is a hindered phenol, and the Mannich Base comprises N-[3,5-di-t-butyl-4-hydroxybenzyl]-mixed C₁₂ to C₁₄ t-alkyl amines, N,N-dimethyl-3,5-di-t-­butyl-4-hydroxybenzylamine, a compound of the formula:
Figure imgb0012
where R₁ and R₂ are independently selected from hydrogen, t-butyl, t-amyl and isopropyl provided that at least one of R₁ and R₂ is t-butyl, t-amyl, or iso­propyl, or a compound of the formula:
Figure imgb0013
where R₁ and R₂ are independently selected from hydrogen, t-butyl, t-amyl and isopropyl provided that at least one of R₁ and R₂ is t-butyl, t-amyl, or iso­propyl.
5. The concentrate of any of claims 1-3 wherein the phenol is a p-alkylphenol, and the Mannich Base comprises N,N-dimethyl-N′-[2-hydroxy-5-dodecylbenzyl]-­1,3-diaminopropane.
6. The concentrate of claim 2 wherein the metal deactivator is N,N′-disalicylidene-1,2-propylenediamine and the Mannich Base is the reaction product of formal­dehyde, 2,6-di-t-butyl phenol and an amine selected from 1,3-diaminopropane, 1,2-diaminopropane, mixed C₁₂-C₁₄ t-alkyl amines, and dimethylamine.
7. The concentrate of claim 2 wherein the metal deactivator is N,N′-disalicylidene-1,2-propylenediamine and the Mannich Base is the reaction product of formal­dehyde, p-dodecyl phenol, and N,N-dimethyl-1,3-diamino­propane.
8. A fuel composition comprising middle distillate fuel containing from 3 to 1500 mgs/liter of the concen­trate of any of claims 1-7.
9. A fuel composition comprising a middle distil­late fuel and from 1 to 1400 mgs/liter N,N-dimethylcyclo­hexylamine, from 0 to 400 mgs/liter N,N-di(ortho-hydroxy­arylidene)-1,2-alkylenediamine and from 1 to 1100 mgs/­liter of a Mannich Base which is the reaction product of an aldehyde, an amine and an alkyl phenol selected from (a) hindered phenol having the formula:
Figure imgb0014
where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
Figure imgb0015
where R₄ is C₉ to C₃₀ alkyl.
10. The fuel composition of claim 9 wherein the aldehyde is formaldehyde and the amine is selected from one or more of:
A. alkyl monoamines of the formula;
Figure imgb0016
where R₅ is selected from H and C₁ to C₅ alkyl and R₆ is selected from C₁ to C₁₄ alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
B. alkyl diamines of the formula;
Figure imgb0017
where R₅ is selected from H and C₁ to C₅ alkyl R₈ is C₁ to C₆ alkylene and A and B are in­dependently selected from H, C₁ to C₅ alkyl, mono­hydroxysubstituted C₁ to C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
D. cyclic amines of the formula;
Figure imgb0018
where n and m are independently intergers from 1 to 3, X is selected from CH₂, O, S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10.
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408087A1 (en) 1989-03-02 1991-01-16 Ethyl Petroleum Additives, Inc. Mannich bases useful in middle distillate fuel having improved storage stability
EP0482253A1 (en) * 1990-10-23 1992-04-29 Ethyl Petroleum Additives Limited Environmentally friendly fuel compositions and additives therefor
EP0534668A1 (en) * 1991-09-24 1993-03-31 Betz Europe, Inc. Stabilization of gasoline mixtures
US5575823A (en) * 1989-12-22 1996-11-19 Ethyl Petroleum Additives Limited Diesel fuel compositions
EP0758661A2 (en) * 1995-07-28 1997-02-19 Asahi Denka Kogyo Kabushiki Kaisha Curable epoxy resin compositions
US5944858A (en) * 1990-09-20 1999-08-31 Ethyl Petroleum Additives, Ltd. Hydrocarbonaceous fuel compositions and additives therefor
WO2002077130A2 (en) * 2001-03-26 2002-10-03 The Associated Octel Company Limited Composition
GB2453248A (en) * 2007-09-27 2009-04-01 Innospec Ltd Diesel fuel compositions
WO2009040584A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
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EP0956328B2 (en) 1996-10-11 2010-07-07 Infineum USA L.P. Fuel compositions with lubricity additives
WO2013174619A1 (en) * 2012-05-25 2013-11-28 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
US8663344B2 (en) 2007-08-24 2014-03-04 Albemarle Corporation Antioxidant blends suitable for use in biodiesels
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007031461A1 (en) * 2007-07-05 2009-01-08 Sappok, Manfred, Dipl.-Phys. Dr. Process for stabilizing heating oil or diesel oil, in particular from the depolymerization of hydrocarbon-containing residues
US20110146139A1 (en) * 2008-09-17 2011-06-23 Marc-Andre Poirier Method for improving the oxidation stability of biodiesel as measured by the rancimat test

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2928790A (en) * 1956-10-03 1960-03-15 Ethyl Corp Petroleum hydrocarbon oil stabilized against oxidative deterioration
US3701641A (en) * 1969-08-29 1972-10-31 Cities Service Oil Co Stabilized distillate hydrocarbon fuel oil compositions and additives therefor
US4025316A (en) * 1974-11-06 1977-05-24 Exxon Research And Engineering Company Mannich base reaction products useful as liquid hydrocarbon additives
US4166726A (en) * 1977-12-16 1979-09-04 Chevron Research Company Diesel fuel containing polyalkylene amine and Mannich base
US4172707A (en) * 1975-09-12 1979-10-30 E. I. Du Pont De Nemours & Company Mannich bases containing tertiary amines
EP0182940A1 (en) * 1984-11-13 1986-06-04 Mobil Oil Corporation Mannich base oil additives
EP0261795A1 (en) * 1986-09-05 1988-03-30 Betz Europe, Inc. Methods for deactivating metallic species in hydrocarbon fluids
EP0294045A2 (en) * 1987-05-11 1988-12-07 Exxon Chemical Patents Inc. Amine compatibility aids in lubricating oil compositions
US9442791B2 (en) * 2014-11-07 2016-09-13 International Business Machines Corporation Building an intelligent, scalable system dump facility

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2984550A (en) 1956-09-06 1961-05-16 Nalco Chemical Co Color stabilization of petroleum oils and compositions therefor
US3502671A (en) * 1964-03-02 1970-03-24 Commercial Solvents Corp Selected n-substituted diazoles and diazines and processes for preparing same
US3446808A (en) * 1964-05-25 1969-05-27 Universal Oil Prod Co Borates of n-hydroxyalkyl-nitrogen-heterocyclic saturated compounds
US3490882A (en) 1966-08-11 1970-01-20 Du Pont Stabilized distillate fuel oils and additive compositions therefor
US3442791A (en) * 1966-11-17 1969-05-06 Betz Laboratories Anti-foulant agents for petroleum hydrocarbons
US3634575A (en) * 1968-10-02 1972-01-11 Celanese Corp Melt extrusion of acrylonitrile polymers
US3634515A (en) * 1968-11-08 1972-01-11 Standard Oil Co Alkylene polyamide formaldehyde
US3725480A (en) * 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US4501595A (en) 1984-05-25 1985-02-26 Texaco Inc. Middle distillate fuel oil of improved storage stability containing condensate of Mannich base and alkenyl succinic acid anhydride
US4533361A (en) 1984-10-09 1985-08-06 Texaco Inc. Middle distillate containing storage stability additive
US4668412A (en) * 1985-06-27 1987-05-26 Texaco Inc. Lubricating oil containing dispersant VII and pour depressant
CA2010183A1 (en) 1989-03-02 1990-09-02 John G. Bostick Middle distillate fuel having improved storage stability

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2928790A (en) * 1956-10-03 1960-03-15 Ethyl Corp Petroleum hydrocarbon oil stabilized against oxidative deterioration
US3701641A (en) * 1969-08-29 1972-10-31 Cities Service Oil Co Stabilized distillate hydrocarbon fuel oil compositions and additives therefor
US4025316A (en) * 1974-11-06 1977-05-24 Exxon Research And Engineering Company Mannich base reaction products useful as liquid hydrocarbon additives
US4172707A (en) * 1975-09-12 1979-10-30 E. I. Du Pont De Nemours & Company Mannich bases containing tertiary amines
US4166726A (en) * 1977-12-16 1979-09-04 Chevron Research Company Diesel fuel containing polyalkylene amine and Mannich base
EP0182940A1 (en) * 1984-11-13 1986-06-04 Mobil Oil Corporation Mannich base oil additives
EP0261795A1 (en) * 1986-09-05 1988-03-30 Betz Europe, Inc. Methods for deactivating metallic species in hydrocarbon fluids
EP0294045A2 (en) * 1987-05-11 1988-12-07 Exxon Chemical Patents Inc. Amine compatibility aids in lubricating oil compositions
US9442791B2 (en) * 2014-11-07 2016-09-13 International Business Machines Corporation Building an intelligent, scalable system dump facility

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408087A1 (en) 1989-03-02 1991-01-16 Ethyl Petroleum Additives, Inc. Mannich bases useful in middle distillate fuel having improved storage stability
US5575823A (en) * 1989-12-22 1996-11-19 Ethyl Petroleum Additives Limited Diesel fuel compositions
US5944858A (en) * 1990-09-20 1999-08-31 Ethyl Petroleum Additives, Ltd. Hydrocarbonaceous fuel compositions and additives therefor
EP0482253A1 (en) * 1990-10-23 1992-04-29 Ethyl Petroleum Additives Limited Environmentally friendly fuel compositions and additives therefor
EP0534668A1 (en) * 1991-09-24 1993-03-31 Betz Europe, Inc. Stabilization of gasoline mixtures
US5783644A (en) * 1995-07-28 1998-07-21 Asahi Denka Kogyo K.K. Curable epoxy resin composition
EP0758661A3 (en) * 1995-07-28 1997-07-23 Asahi Denka Kogyo Kk Curable epoxy resin compositions
EP0758661A2 (en) * 1995-07-28 1997-02-19 Asahi Denka Kogyo Kabushiki Kaisha Curable epoxy resin compositions
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WO2002077130A2 (en) * 2001-03-26 2002-10-03 The Associated Octel Company Limited Composition
WO2002077130A3 (en) * 2001-03-26 2003-04-17 Ass Octel Composition
EP2052061A2 (en) * 2006-07-11 2009-04-29 Innospec Fuel Specialties LLC Stabilizer compositions for blends of petroleum and renewable fuels
EP2052061A4 (en) * 2006-07-11 2012-01-25 Innospec Fuel Specialties Llc Stabilizer compositions for blends of petroleum and renewable fuels
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CN102037104A (en) * 2007-09-27 2011-04-27 因诺斯佩克有限公司 Fuel compositions
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WO2013174619A1 (en) * 2012-05-25 2013-11-28 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
AU2013265575B2 (en) * 2012-05-25 2017-06-15 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
US9388354B2 (en) 2012-11-06 2016-07-12 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
WO2014023853A3 (en) * 2012-11-06 2014-04-10 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
CN113527163A (en) * 2021-08-10 2021-10-22 新乡市瑞丰新材料股份有限公司 Preparation method of alkylphenol detergent

Also Published As

Publication number Publication date
EP0408087A1 (en) 1991-01-16
EP0385633B1 (en) 1993-04-07
AU619957B2 (en) 1992-02-06
CA2010183A1 (en) 1990-09-02
DE69001269T2 (en) 1993-07-22
JPH02292392A (en) 1990-12-03
AU5060390A (en) 1990-09-06
DE69001269D1 (en) 1993-05-13

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