Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/228—Organic 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
  • C10L1/2283—Organic 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2493—Organic 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)
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• 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)

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• 1990
  • 1990-02-15 CA CA 2010183 patent/CA2010183A1/fr not_active Abandoned
  • 1990-02-20 DE DE1990601269 patent/DE69001269T2/de not_active Expired - Fee Related
  • 1990-02-20 EP EP90116830A patent/EP0408087A1/fr not_active Ceased
  • 1990-02-20 EP EP90301791A patent/EP0385633B1/fr not_active Expired - Lifetime
  • 1990-03-01 JP JP4736490A patent/JPH02292392A/ja active Pending
  • 1990-03-01 AU AU50603/90A patent/AU619957B2/en not_active Ceased

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