Note: Descriptions are shown in the official language in which they were submitted.
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.
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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
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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,
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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
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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.
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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
