EP0385633A1 - Middle distillate fuel having improved storage stability - Google Patents
Middle distillate fuel having improved storage stability Download PDFInfo
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- 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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- alkyl
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- butyl
- phenol
- fuel
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Classifications
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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
- C10L1/221—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, 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
-
- 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
-
- 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
- C10L1/232—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, 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
- C10L1/18—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/228—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, 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
- C10L1/24—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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Abstract
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:
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;
- B. alkyl diamines of the formula;
- C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and - D. cyclic amines of the formula;
- 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:
- 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.
- 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.
- 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.
- 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.
- 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.
- 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)
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US31874889A | 1989-03-02 | 1989-03-02 | |
US318748 | 1989-03-02 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP90116830A Division-Into EP0408087A1 (en) | 1989-03-02 | 1990-02-20 | Mannich bases useful in middle distillate fuel having improved storage stability |
EP90116830A Division EP0408087A1 (en) | 1989-03-02 | 1990-02-20 | Mannich bases useful in middle distillate fuel having improved storage stability |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0385633A1 true EP0385633A1 (en) | 1990-09-05 |
EP0385633B1 EP0385633B1 (en) | 1993-04-07 |
Family
ID=23239444
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90301791A Expired - Lifetime EP0385633B1 (en) | 1989-03-02 | 1990-02-20 | Middle distillate fuel having improved storage stability |
EP90116830A Ceased EP0408087A1 (en) | 1989-03-02 | 1990-02-20 | Mannich bases useful in middle distillate fuel having improved storage stability |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP90116830A Ceased EP0408087A1 (en) | 1989-03-02 | 1990-02-20 | Mannich bases useful in middle distillate fuel having improved storage stability |
Country Status (5)
Country | Link |
---|---|
EP (2) | EP0385633B1 (en) |
JP (1) | JPH02292392A (en) |
AU (1) | AU619957B2 (en) |
CA (1) | CA2010183A1 (en) |
DE (1) | DE69001269T2 (en) |
Cited By (17)
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 |
WO2009040585A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
EP2052061A2 (en) * | 2006-07-11 | 2009-04-29 | Innospec Fuel Specialties LLC | Stabilizer compositions for blends of petroleum and renewable fuels |
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 |
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 |
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 |
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 |
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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 |
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- 1990-02-20 EP EP90116830A patent/EP0408087A1/en not_active Ceased
- 1990-02-20 DE DE1990601269 patent/DE69001269T2/en not_active Expired - Fee Related
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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 |
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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 |
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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 |
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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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