CA2079049A1 - Fuel compositions - Google Patents
Fuel compositionsInfo
- Publication number
- CA2079049A1 CA2079049A1 CA 2079049 CA2079049A CA2079049A1 CA 2079049 A1 CA2079049 A1 CA 2079049A1 CA 2079049 CA2079049 CA 2079049 CA 2079049 A CA2079049 A CA 2079049A CA 2079049 A1 CA2079049 A1 CA 2079049A1
- Authority
- CA
- Canada
- Prior art keywords
- fuel
- carbon atoms
- additive
- group
- alkoxylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
-
- 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
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
-
- 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
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
-
- 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
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
Abstract
CASE: EI-6032 FUEL COMPOSITIONS
Abstract Distillate fuels containing water are dehazed using an additive comprising an alkoxylated amine and an alkoxylated alcohol.
Abstract Distillate fuels containing water are dehazed using an additive comprising an alkoxylated amine and an alkoxylated alcohol.
Description
PATENTS
2~ 9 CASE EI-6032 FUEL COMPOSITIONS
This invention relates to additives, fuel compositions and methods for dehazing distillate fuels.
Distillate fuels, such as gasoline, jet fuels, and diesel fuels typically contain dissolved water under processing conditions. As the fuel cools, the water can give the fuel a hazy appearence. Such fuels containing dissolved water may also be compounded with a variety of additives. While these additives provide enhanced performance of the fuels, some of the additives further decrease the tolerance of the fuels towards the dissolved water. Water intolerance can lead to fuels having hazy appearance which appearance is quite undesirable.
A variety of compounds and methods have been proposed for reducing or eliminating the water intolerance of fuel thus providing a non-hazy fuel. One method includes the addition to fuel of a reaction product formed by reacting a phenol-formalde-hyde resin with an alpha-olefin epoxide and then reacting the product with alkylene oxides such as ethylene oxide, propylene oxide, or combinations thereof according to U.S. 4,046,521. U.S.
4,002,558 discloses the use of halides or nitrates of calcium, magnesium, cadmium, copper or nickel in water miscible, fuel immiscible solvents, especially alcohols or glycols for removing water haze from distillate fuel. Organosiloxanes are also useful for dehazing distillate fuels according to U.S. Pat. Nos.
4,460,380; 4,818,251; and 4,854,938.
Methods and compositions for preparing non-hazy blends of fuels containing water are disclosed in U.S. Pat. Nos.
4,283,203; 4,397,655; 4,508,541; 4,565,548; 4,568,354; 4,568,355;
4,599,088; 4,608,057; and in G.B. 2,016,517 and Chinese patent 1 r~ A A ~ rT ~ A ~ n n ~ o o ,~
2 ~ n g CASE: EI-6032 of alkylphenol and ethylene oxide having the structural formula as follows:
R(cH2cH2o)xH
wherein R is an alkylphenol group where the alkyl group has g to 24 carbons, and x i5 an integer form 6-10.
Emulsified fuels containinq a polyethenoxy derivative of an alkylphenol are disclosed in U.S. 2,920,948. Fuel emulsions containing water and certain surfactants are disclosed in U.S. 3,876,391. U.S. 5,000,757 relates to a method for forming emulsions of fuel oil in water using an ethoxylated alkyl phenol surfactant among other non-ionic surfactants.
U.S. 4,795,478 discloses a process for forming a hydrocarbon-in-water emulsion by using a first emulsifier selected from ethoxylated alkyl phenol, ethoxylated alcohols, ethoxylated sorbitan esters and their mixtures and a second emulsifier chosen from nonionic surfactants and alkalies.
U.S. 4,460,379 relates to middle distillate fuel compositions comprising a minor stabilizing amount of a hydro-carbyl polyoxypropylene di(polyoxyethylene) amine. And U.S.
4,391,610 discloses the use of a dialkoxylated alkyl polyoxyalkyl primary amine as a corrosion inhibitor in gasolines, optionally containing at least one alcohol.
U.S. Pat. Nos. 3,822,119; 3,988,122; 4,384,872;
4,410,334; and 4,565,548 disclose fuel mixtures containing water, alcohols and additives.
Stabilized fuels containing the condensation product of an alkanolamine and the reaction product of a terpene and a compound selected from an ~ unsaturated polycarboxylic acid are disclosed in U.S. Pat. Nos. 2,974,023 and 2,974,024. U.S.
.9 CASE: EI-6032 4,154,580 discloses a method for preparing stabilized gasoline-alcohol fuel blends. U.S. 4,392,867 discloses the use of certain amines of the formula (R(OR1)n)a-NH3a wherein R contains 4-30 carbon atoms and is selected from the group consisting of alkyl, alkenyl, alkaryl, arakyl, cycloalkyl and aryl groups and R1 is a divalent hydrocarbon group containing 1-30 carbon atoms and is selected from the group consisting of alkylene, alkenylene, aral-kylene, cycloalkylene, and arylene groups, n is an integer 2-30 and a is an integer 1-3, as additives for fuels containing alcohol and water. Middle distillate fuel compositions with increased storage stability, containing an additive prepared by reacting a hydrocarbon-substituted mono primary amine or a hydrocarbon-substituted mono primary etheramine; a dibasic acid anhydride; and an N-alkyl alkylene diamine are disclosed in U.S.
4,689,051. Other storage stabilizer additives for middle distillate fuels are disclosed in U.S. 5,000,759.
There continues to be a need for additives and methods for clarifying hazy fuels without requiring that water be removed from the fuel. Such additives should be readily miscible with the fuel to be dehazed without adversely affecting the performance of the fuel.
This invention provides, inter alia, a fuel composition comprising a major portion of distillate fuel and a minor amount of additive mixture containing (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol wherein the amount of additive mixture is sufficient to dehaze the fuel.
It has been found the additives of this invention are useful in clarifying hazy fuels, without the need to remove water from the fuel.
2- CASE: EI-6032 In another embodiment, this invention provides an additive concentrate for dehazing middle distillate fuels comprising (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
In still another embodiment, this invention provides a method for dehazing a middle distillate fuel comprising providing an amount of additive mixture sufficient to dehaze the fuel, wherein the additive mixture comprises (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
A wide variety of distillate petroleum fuels containing a minor amount of water can be dehazed according to this invention. By minor amount of water is meant less than about 1 percent water by weight based on the total weight of the fuel.
In general, the preferred fuels are mixtures of hydrocarbons which fall within the diesel fuel boiling range, typically 160 C
to 370 C. These fuels are often referred to as middle distillate fuels since they comprise the fractions which distill after gasoline. This invention is not limited, however to diesel fuels as other fuels such as gasoline, jet fuels, aircraft fuels, and marine fuels which can be dehazed with the compositions and methods of this invention are also included.
The base fuel to be dehazed will normally contain an amount of additive in the range of 0.01 to 5 percent by weight, preferably from 0.02 to 3 percent by weight, and most preferably from 0.10 to 2 percent by weight based on the total weight of the fuel plus additive. Such quantities are normally sufficient to reduce the haze in diesel fuels containing less than 1 percent by weight of water.
The additive mixture can be formed in situ in the fuel by adding the individual components, in any order, to the base ~ 9 CASE: EI-6032 fuel. It is preferred, however, to form an additive concentrate containing at least one alkoxylated amine and at least one alkoxylated alcohol, then add this additive concentrate to the base fuel to be dehazed. The additive concentrate will normally contain from 30 to 85 parts of one or more alkoxy-lated amines, and from 15 to 70 parts of one or more alkoxylated alcohols.
Preferably, the additive concentrate contains from 50 to 75 parts of one or more alkoxy-lated amines and from 25 to 50 parts of one or more alkoxylated alcohols. Most preferably, an additive concentrate is formed by admixing 55 to 70 parts of one or more alkoxylated amines with 30 to 45 parts of one or more alkoxylated alcohols. For purposes of this invention, the additive concentrate can be formed using any commercially available mixing or blending equipment.
The alkoxylated amines useful in the compositions and methods of this invention can be represented by the following formula ~ ( R 1 ) x H
R - N
( R 2 ) y H
wherein R is an alkyl group of from 1 to 50 carbon atoms and each of R1 and R2 is alike or different and is an alky-lene group of from 1 to 50 carbon atoms, and the sum of x f y iS an integer from 2-40. In a preferred embodiment, R is an alkyl having from 10 to 18 carbon atoms, and each of R1 and Rz alike or different and is an ethylene, propylene, butylene, isopropylene, or isobutylene group. In a particularly preferred embodiment, R is an alkyl having from 12 to 14 carbon atoms, Rl and Rz are ethylene groups, and the sum of x + y is 2. The amines represented by the above formula are generally available as mixtures of amines. For the purposes of this invention, 2~ " 9 CASE: EI-6032 alkoxylated amine will be used to mean one or a mixture of two or more alkoxylated amines predominant in a preferred amine.
Examples of useful alkoxylated amines include ethoxy-lated fatty amines such as ethoxylated decylamine, ethoxylated dodecylamine, ethoxylated tetradecylamine, ethoxylated cocoalkyl-amine, ethoxylated tallowalkylamine, ethoxylated soyaalkylamine, and ethoxylated octadecylamine. Diamines may also be used including ethoxylated N-decyl-1,3-diaminopropane, ethoxy-lated N-dodecyl-1,3-diaminopropane, ethoxylated N-cocoalkyl-1,3-diaminopropane, ethoxylated N-soyaalkyl-1,3-diaminopropane, ethoxylated N-tallow-1,3-diaminopropane, and ethoxylated N-octadecyl-1,3-diaminopropane.
Alkoxylated alcohols useful in the compositions and process of this invention include one or a mixture of alkoxylated alcohols of the formula R4(0Rs)~(OR6)~0H
wherein R4 is an alkyl or cycloalkyl group of from 1 to 40 carbon atoms, and each of ~ and R6 is alike or different and is an alkylene, or cycloalkylene group having from 1 to 40 carbon atoms. In a preferred embodiment, R4 is an alkyl group having from 8 to 18 carbon atoms; each of Rs~ and R6 is alike or different and is an ethylene, propylene, butylene, isopropylene, or isobutylene group; and the sum of w + z is in the range of 2 to 20. In a particularly preferred embodiment, R4 is an alkyl group having from 10 to 14 carbon atoms, R5 is an ethylene group, R6 is a propy-lene group, and the sum of w + z is in the range of 6 to 12. The preferred alkoxylated alcohols are mixtures of ethoxylated propoxylated alcohols, most preferably ethoxylated propoxylated lauryl alcohols.
The additives of this invention are desirably added to hot fuels containing dissolved water however, such additives may 2~ 9 CASE: EI-6032 also be added to fuels at room temperature or lower. Whether the additive is added to the fuel at room temperature or lower, or to hot fuel, it is particularly preferred that the fuel temperature be in the range of from 30 to 90 C prior to or subsequent to addition of the additive of this invention in order to more effectively dehaze the fuel.
Conventional additives and blending agents for diesel fuel may be present in the fuel compositions of this invention or may be added subsequent to addition of the additives of this invention. For example, the fuels of this invention may contain conventional quantities of such conventional additives as cetane improvers, friction modifiers, detergents, antioxidants, and heat stabilizers. Similarly the fuels may contain suitable minor amounts of conventional fuel blending components such as methanol, ethanol, and dialkyl ethers.
Example 1 The effectiveness of the additive for reducing haze in diesel fuels was demonstrated by first preparing a hazy fuel mixture containing 150 mL of test diesel fuel and one half (1/2) mL of water. The fuel and water were stirred in a Waring blender for 15 seconds and the resulting mixture was stored at 43C for 16 hours. After storing, the mixture was cooled to 5.5C and observed for haze. Haze was determined by measuring the amount of light transmittance through the fuel mixture with a Milton Roy Spectronic 20D spectrometer operating at a wave length of 540 nanometers. Light transmittance is expressed as percent light transmitted. Clearer fuels are those with the higher percent transmittance.
Having prepared a hazy fuel mixture, the dehazing additive was added while stirring the fuel mixture, and the fuel was heated to about 43 C. After letting the mixture cool to 2 ~ 9 CASE: EI-6032 about 6 C, light transmittance through the sample was measured.
Results of the use of two different additives is illustrated in the following Table 1. Additive #1 was a mixture containing 54%
by weight ETHOMEEN C/12 and 46% by weight ETHOMEEN C/20 (Trademarks of Akzo Chemical Co.) ethoxylated amines. Additive #2 was composed of 63% by weight of ETHOMEEN C/12 and 37% by weight of ALKASURF LA-EP38 (Trademark of Alkaril, Inc.) alkylated alcohol. Fuel #1 was diesel fuel obtained from La Plata, Argentina. Fuel #2 was diesel fuel obtained from Lujan De Cuyo, Argentina.
Table 1 , Additive Light Amount VisualTransmitted ¦ Sample Fuel No. Additive (vol. %) Appearance (percent) ¦ 1 1 none 0.0 Hazy 65.0 ¦ 2 1 #1 1.0 Hazy 67.6 1 3 #2 1.5 Clear 70.8 I
¦ 4 2 none 0.0 Hazy 68.8 r 2 #1 1.0 Hazy 75.0 ¦ 6 2 #2 1.5 Clear 83.2 Example 2 The amount of additive #2 used in Example 1 was reduced to determine the minimum amount necessary to dehaze the above fuels. The results are illustrated in Table 2.
z~ 9 CASE: EI-6032 Table 2 Additive Light Amount Visual Transmitted Sample Fuel No. (ppm) Appearance (percent) 1 1 250 Hazy 80.8 2 1 100 Hazy 75.4 3 2 250 ~ Clear 87.0 4 2 100 Hazy 81.2
This invention relates to additives, fuel compositions and methods for dehazing distillate fuels.
Distillate fuels, such as gasoline, jet fuels, and diesel fuels typically contain dissolved water under processing conditions. As the fuel cools, the water can give the fuel a hazy appearence. Such fuels containing dissolved water may also be compounded with a variety of additives. While these additives provide enhanced performance of the fuels, some of the additives further decrease the tolerance of the fuels towards the dissolved water. Water intolerance can lead to fuels having hazy appearance which appearance is quite undesirable.
A variety of compounds and methods have been proposed for reducing or eliminating the water intolerance of fuel thus providing a non-hazy fuel. One method includes the addition to fuel of a reaction product formed by reacting a phenol-formalde-hyde resin with an alpha-olefin epoxide and then reacting the product with alkylene oxides such as ethylene oxide, propylene oxide, or combinations thereof according to U.S. 4,046,521. U.S.
4,002,558 discloses the use of halides or nitrates of calcium, magnesium, cadmium, copper or nickel in water miscible, fuel immiscible solvents, especially alcohols or glycols for removing water haze from distillate fuel. Organosiloxanes are also useful for dehazing distillate fuels according to U.S. Pat. Nos.
4,460,380; 4,818,251; and 4,854,938.
Methods and compositions for preparing non-hazy blends of fuels containing water are disclosed in U.S. Pat. Nos.
4,283,203; 4,397,655; 4,508,541; 4,565,548; 4,568,354; 4,568,355;
4,599,088; 4,608,057; and in G.B. 2,016,517 and Chinese patent 1 r~ A A ~ rT ~ A ~ n n ~ o o ,~
2 ~ n g CASE: EI-6032 of alkylphenol and ethylene oxide having the structural formula as follows:
R(cH2cH2o)xH
wherein R is an alkylphenol group where the alkyl group has g to 24 carbons, and x i5 an integer form 6-10.
Emulsified fuels containinq a polyethenoxy derivative of an alkylphenol are disclosed in U.S. 2,920,948. Fuel emulsions containing water and certain surfactants are disclosed in U.S. 3,876,391. U.S. 5,000,757 relates to a method for forming emulsions of fuel oil in water using an ethoxylated alkyl phenol surfactant among other non-ionic surfactants.
U.S. 4,795,478 discloses a process for forming a hydrocarbon-in-water emulsion by using a first emulsifier selected from ethoxylated alkyl phenol, ethoxylated alcohols, ethoxylated sorbitan esters and their mixtures and a second emulsifier chosen from nonionic surfactants and alkalies.
U.S. 4,460,379 relates to middle distillate fuel compositions comprising a minor stabilizing amount of a hydro-carbyl polyoxypropylene di(polyoxyethylene) amine. And U.S.
4,391,610 discloses the use of a dialkoxylated alkyl polyoxyalkyl primary amine as a corrosion inhibitor in gasolines, optionally containing at least one alcohol.
U.S. Pat. Nos. 3,822,119; 3,988,122; 4,384,872;
4,410,334; and 4,565,548 disclose fuel mixtures containing water, alcohols and additives.
Stabilized fuels containing the condensation product of an alkanolamine and the reaction product of a terpene and a compound selected from an ~ unsaturated polycarboxylic acid are disclosed in U.S. Pat. Nos. 2,974,023 and 2,974,024. U.S.
.9 CASE: EI-6032 4,154,580 discloses a method for preparing stabilized gasoline-alcohol fuel blends. U.S. 4,392,867 discloses the use of certain amines of the formula (R(OR1)n)a-NH3a wherein R contains 4-30 carbon atoms and is selected from the group consisting of alkyl, alkenyl, alkaryl, arakyl, cycloalkyl and aryl groups and R1 is a divalent hydrocarbon group containing 1-30 carbon atoms and is selected from the group consisting of alkylene, alkenylene, aral-kylene, cycloalkylene, and arylene groups, n is an integer 2-30 and a is an integer 1-3, as additives for fuels containing alcohol and water. Middle distillate fuel compositions with increased storage stability, containing an additive prepared by reacting a hydrocarbon-substituted mono primary amine or a hydrocarbon-substituted mono primary etheramine; a dibasic acid anhydride; and an N-alkyl alkylene diamine are disclosed in U.S.
4,689,051. Other storage stabilizer additives for middle distillate fuels are disclosed in U.S. 5,000,759.
There continues to be a need for additives and methods for clarifying hazy fuels without requiring that water be removed from the fuel. Such additives should be readily miscible with the fuel to be dehazed without adversely affecting the performance of the fuel.
This invention provides, inter alia, a fuel composition comprising a major portion of distillate fuel and a minor amount of additive mixture containing (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol wherein the amount of additive mixture is sufficient to dehaze the fuel.
It has been found the additives of this invention are useful in clarifying hazy fuels, without the need to remove water from the fuel.
2- CASE: EI-6032 In another embodiment, this invention provides an additive concentrate for dehazing middle distillate fuels comprising (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
In still another embodiment, this invention provides a method for dehazing a middle distillate fuel comprising providing an amount of additive mixture sufficient to dehaze the fuel, wherein the additive mixture comprises (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
A wide variety of distillate petroleum fuels containing a minor amount of water can be dehazed according to this invention. By minor amount of water is meant less than about 1 percent water by weight based on the total weight of the fuel.
In general, the preferred fuels are mixtures of hydrocarbons which fall within the diesel fuel boiling range, typically 160 C
to 370 C. These fuels are often referred to as middle distillate fuels since they comprise the fractions which distill after gasoline. This invention is not limited, however to diesel fuels as other fuels such as gasoline, jet fuels, aircraft fuels, and marine fuels which can be dehazed with the compositions and methods of this invention are also included.
The base fuel to be dehazed will normally contain an amount of additive in the range of 0.01 to 5 percent by weight, preferably from 0.02 to 3 percent by weight, and most preferably from 0.10 to 2 percent by weight based on the total weight of the fuel plus additive. Such quantities are normally sufficient to reduce the haze in diesel fuels containing less than 1 percent by weight of water.
The additive mixture can be formed in situ in the fuel by adding the individual components, in any order, to the base ~ 9 CASE: EI-6032 fuel. It is preferred, however, to form an additive concentrate containing at least one alkoxylated amine and at least one alkoxylated alcohol, then add this additive concentrate to the base fuel to be dehazed. The additive concentrate will normally contain from 30 to 85 parts of one or more alkoxy-lated amines, and from 15 to 70 parts of one or more alkoxylated alcohols.
Preferably, the additive concentrate contains from 50 to 75 parts of one or more alkoxy-lated amines and from 25 to 50 parts of one or more alkoxylated alcohols. Most preferably, an additive concentrate is formed by admixing 55 to 70 parts of one or more alkoxylated amines with 30 to 45 parts of one or more alkoxylated alcohols. For purposes of this invention, the additive concentrate can be formed using any commercially available mixing or blending equipment.
The alkoxylated amines useful in the compositions and methods of this invention can be represented by the following formula ~ ( R 1 ) x H
R - N
( R 2 ) y H
wherein R is an alkyl group of from 1 to 50 carbon atoms and each of R1 and R2 is alike or different and is an alky-lene group of from 1 to 50 carbon atoms, and the sum of x f y iS an integer from 2-40. In a preferred embodiment, R is an alkyl having from 10 to 18 carbon atoms, and each of R1 and Rz alike or different and is an ethylene, propylene, butylene, isopropylene, or isobutylene group. In a particularly preferred embodiment, R is an alkyl having from 12 to 14 carbon atoms, Rl and Rz are ethylene groups, and the sum of x + y is 2. The amines represented by the above formula are generally available as mixtures of amines. For the purposes of this invention, 2~ " 9 CASE: EI-6032 alkoxylated amine will be used to mean one or a mixture of two or more alkoxylated amines predominant in a preferred amine.
Examples of useful alkoxylated amines include ethoxy-lated fatty amines such as ethoxylated decylamine, ethoxylated dodecylamine, ethoxylated tetradecylamine, ethoxylated cocoalkyl-amine, ethoxylated tallowalkylamine, ethoxylated soyaalkylamine, and ethoxylated octadecylamine. Diamines may also be used including ethoxylated N-decyl-1,3-diaminopropane, ethoxy-lated N-dodecyl-1,3-diaminopropane, ethoxylated N-cocoalkyl-1,3-diaminopropane, ethoxylated N-soyaalkyl-1,3-diaminopropane, ethoxylated N-tallow-1,3-diaminopropane, and ethoxylated N-octadecyl-1,3-diaminopropane.
Alkoxylated alcohols useful in the compositions and process of this invention include one or a mixture of alkoxylated alcohols of the formula R4(0Rs)~(OR6)~0H
wherein R4 is an alkyl or cycloalkyl group of from 1 to 40 carbon atoms, and each of ~ and R6 is alike or different and is an alkylene, or cycloalkylene group having from 1 to 40 carbon atoms. In a preferred embodiment, R4 is an alkyl group having from 8 to 18 carbon atoms; each of Rs~ and R6 is alike or different and is an ethylene, propylene, butylene, isopropylene, or isobutylene group; and the sum of w + z is in the range of 2 to 20. In a particularly preferred embodiment, R4 is an alkyl group having from 10 to 14 carbon atoms, R5 is an ethylene group, R6 is a propy-lene group, and the sum of w + z is in the range of 6 to 12. The preferred alkoxylated alcohols are mixtures of ethoxylated propoxylated alcohols, most preferably ethoxylated propoxylated lauryl alcohols.
The additives of this invention are desirably added to hot fuels containing dissolved water however, such additives may 2~ 9 CASE: EI-6032 also be added to fuels at room temperature or lower. Whether the additive is added to the fuel at room temperature or lower, or to hot fuel, it is particularly preferred that the fuel temperature be in the range of from 30 to 90 C prior to or subsequent to addition of the additive of this invention in order to more effectively dehaze the fuel.
Conventional additives and blending agents for diesel fuel may be present in the fuel compositions of this invention or may be added subsequent to addition of the additives of this invention. For example, the fuels of this invention may contain conventional quantities of such conventional additives as cetane improvers, friction modifiers, detergents, antioxidants, and heat stabilizers. Similarly the fuels may contain suitable minor amounts of conventional fuel blending components such as methanol, ethanol, and dialkyl ethers.
Example 1 The effectiveness of the additive for reducing haze in diesel fuels was demonstrated by first preparing a hazy fuel mixture containing 150 mL of test diesel fuel and one half (1/2) mL of water. The fuel and water were stirred in a Waring blender for 15 seconds and the resulting mixture was stored at 43C for 16 hours. After storing, the mixture was cooled to 5.5C and observed for haze. Haze was determined by measuring the amount of light transmittance through the fuel mixture with a Milton Roy Spectronic 20D spectrometer operating at a wave length of 540 nanometers. Light transmittance is expressed as percent light transmitted. Clearer fuels are those with the higher percent transmittance.
Having prepared a hazy fuel mixture, the dehazing additive was added while stirring the fuel mixture, and the fuel was heated to about 43 C. After letting the mixture cool to 2 ~ 9 CASE: EI-6032 about 6 C, light transmittance through the sample was measured.
Results of the use of two different additives is illustrated in the following Table 1. Additive #1 was a mixture containing 54%
by weight ETHOMEEN C/12 and 46% by weight ETHOMEEN C/20 (Trademarks of Akzo Chemical Co.) ethoxylated amines. Additive #2 was composed of 63% by weight of ETHOMEEN C/12 and 37% by weight of ALKASURF LA-EP38 (Trademark of Alkaril, Inc.) alkylated alcohol. Fuel #1 was diesel fuel obtained from La Plata, Argentina. Fuel #2 was diesel fuel obtained from Lujan De Cuyo, Argentina.
Table 1 , Additive Light Amount VisualTransmitted ¦ Sample Fuel No. Additive (vol. %) Appearance (percent) ¦ 1 1 none 0.0 Hazy 65.0 ¦ 2 1 #1 1.0 Hazy 67.6 1 3 #2 1.5 Clear 70.8 I
¦ 4 2 none 0.0 Hazy 68.8 r 2 #1 1.0 Hazy 75.0 ¦ 6 2 #2 1.5 Clear 83.2 Example 2 The amount of additive #2 used in Example 1 was reduced to determine the minimum amount necessary to dehaze the above fuels. The results are illustrated in Table 2.
z~ 9 CASE: EI-6032 Table 2 Additive Light Amount Visual Transmitted Sample Fuel No. (ppm) Appearance (percent) 1 1 250 Hazy 80.8 2 1 100 Hazy 75.4 3 2 250 ~ Clear 87.0 4 2 100 Hazy 81.2
Claims (10)
1. An additive concentrate for dehazing middle distillate fuels comprising (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
2. The additive concentrate of Claim 1 wherein the alkoxylated amine is one or a mixture of amines of the formula wherein R is an alkyl group of from 2 to 20 carbon atoms and each of R1, and R2 is alike or different and is an alkylene group of from 2 to 20 carbon atoms, and the sum of x + y is an integer from 2-50.
3. The additive concentrate of Claim 2 wherein R is an alkyl having from 10 to 18 carbon atoms, and each of R1 and R2 is alike or different and is an ethylene or propylene group.
4. The additive concentrate of Claim 3 wherein R is an alkyl group having from 12 to 14 carbon atoms, R1 and R2 are ethylene groups, and the sum of x + y is 2.
5. The additive concentrate of Claim 1 wherein the alkoxylated alcohol is one or a mixture of alcohols of the formula R4(OR5)w(OR6)zOH
wherein R4 is an alkyl or cycloalkyl group having from 2 to 20 carbon atoms and each of R5 and R6 is alike or different and is an alkylene, or cycloalkylene group having from 2 to 20 carbon atoms.
wherein R4 is an alkyl or cycloalkyl group having from 2 to 20 carbon atoms and each of R5 and R6 is alike or different and is an alkylene, or cycloalkylene group having from 2 to 20 carbon atoms.
6. The additive concentrate of Claim 5 wherein R4 is an alkyl group having from 10 to 16 carbon atoms, R5 is an ethylene group, R6 is a propylene group, and the sum of w + z is in the range of 6 to 12.
CASE: EI-6032
CASE: EI-6032
7. The additive concentrate of Claim 1 comprising (i) 2 parts of one or a mixture of ethoxylated amines predominant in an amine of the formula wherein R is an alkyl group having from 12 to 14 carbon atoms, R1 and R2 are ethylene groups, and the sum of x + y is 2; and (ii) 1 part of one or a mixture of alkoxylated alcohols predominant in an alcohol of the formula R4(OR5)w(OR6)zOH
wherein R4 is an alkyl group having from 10 to 16 carbon atoms, R5 is an ethylene group, R6 is a propylene group, and the sum of w + z is in the range of 6 to 12.
wherein R4 is an alkyl group having from 10 to 16 carbon atoms, R5 is an ethylene group, R6 is a propylene group, and the sum of w + z is in the range of 6 to 12.
8. A fuel composition comprising a major portion of distillate fuel and a minor amount of additive mixture containing (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol wherein said amount of additive mixture is sufficient to dehaze said fuel.
9. The fuel composition of Claim 8 wherein the distillate fuel is a middle distillate fuel.
10. A method for dehazing a middle distillate fuel comprising providing an amount of additive mixture sufficient to dehaze said fuel wherein said additive mixture comprises (i) at least one alkoxylated amine and (ii) at least one alkoxylated alcohol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77500891A | 1991-10-11 | 1991-10-11 | |
| US775,008 | 1991-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2079049A1 true CA2079049A1 (en) | 1993-04-12 |
Family
ID=25103033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2079049 Abandoned CA2079049A1 (en) | 1991-10-11 | 1992-09-24 | Fuel compositions |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2079049A1 (en) |
| GB (1) | GB2260337A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9500460D0 (en) * | 1995-01-10 | 1995-03-01 | Exxon Chemical Patents Inc | Fuel compositions |
| 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 |
| WO2014023853A2 (en) | 2012-11-06 | 2014-02-13 | Basf Se | Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3700363A1 (en) * | 1987-01-08 | 1988-07-21 | Basf Ag | FUEL OR LUBRICANT COMPOSITION AND USE OF POLYBUTYL OR POLYISOBUTYL DERIVATIVES IN THE SAME |
| US5197997A (en) * | 1990-11-29 | 1993-03-30 | The Lubrizol Corporation | Composition for use in diesel powered vehicles |
-
1992
- 1992-09-24 CA CA 2079049 patent/CA2079049A1/en not_active Abandoned
- 1992-10-06 GB GB9220997A patent/GB2260337A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB9220997D0 (en) | 1992-11-18 |
| GB2260337A (en) | 1993-04-14 |
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