U.S. patent application number 10/319668 was filed with the patent office on 2004-06-17 for emulsified water blended fuels produced by using a low energy process and novel surfuctant.
Invention is credited to Di Biase, Stephen A., Duncan, David A., Filippini, Brian B., Mullay, John J., Steckel, Thomas F., Westfall, David L..
Application Number | 20040111955 10/319668 |
Document ID | / |
Family ID | 32506679 |
Filed Date | 2004-06-17 |
United States Patent
Application |
20040111955 |
Kind Code |
A1 |
Mullay, John J. ; et
al. |
June 17, 2004 |
Emulsified water blended fuels produced by using a low energy
process and novel surfuctant
Abstract
A novel low energy process to produce water in oil emulsions in
particular water blended fuels by employing a low molecular weight
surfactant with an emulsifier package.
Inventors: |
Mullay, John J.; (Mentor,
OH) ; Westfall, David L.; (Lakewood, OH) ;
Filippini, Brian B.; (Mentor-on-the-Lake, OH) ;
Steckel, Thomas F.; (Chagrin Falls, OH) ; Di Biase,
Stephen A.; (Lakewood, OH) ; Duncan, David A.;
(Ashbourne, GB) |
Correspondence
Address: |
The Lubrizol Corporation
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Family ID: |
32506679 |
Appl. No.: |
10/319668 |
Filed: |
December 13, 2002 |
Current U.S.
Class: |
44/301 |
Current CPC
Class: |
C10L 1/2222 20130101;
C10L 1/2364 20130101; C10L 1/1802 20130101; C10L 1/2225 20130101;
C10L 1/328 20130101; C10L 1/1852 20130101; C10L 1/1881 20130101;
C10L 1/1266 20130101; C10L 1/191 20130101; C10L 1/2641 20130101;
C10L 1/2437 20130101; C10L 1/198 20130101; C10L 1/10 20130101; C10L
1/1985 20130101; C10L 1/224 20130101; C10L 1/19 20130101; C10L
1/2383 20130101; C10L 10/12 20130101; C10L 1/1824 20130101; C09K
23/017 20220101; C10L 1/238 20130101; C10L 1/1883 20130101; C10L
10/02 20130101; C10L 1/1857 20130101; C10L 1/1888 20130101; C10L
1/221 20130101; C10L 1/23 20130101; C10L 1/125 20130101; C10L
1/2658 20130101; C10L 1/1826 20130101; C10L 1/1691 20130101; C10L
1/226 20130101; C10L 1/2387 20130101 |
Class at
Publication: |
044/301 |
International
Class: |
C10L 001/32 |
Claims
What is claimed:
1. An emulsified water in oil composition comprising: A) a fuel; B)
a water; C) a high molecular weight emulsifier; D) a surfactant
having a molecular weight of about less than or equal to about 950
g/mol wherein the surfactant comprises: i) natural fats; ii)
non-ionic and ionic surfactants; iii) co-surfactanta; iv) fatty
acids and their amine salts; or v) combinations thereof; and E)
optionally ammonium nitrate.
2. The composition of claim 2 wherein a fuel is in the range of
about 50% to about 99% by weight of the composition; the water is
in the range of about 1% to about 50% by weight of the composition;
the emulsifier is in the range of about 1% to about 50% by weight
of the composition; and the surfactant in the range of about 0.001%
to about 15% by weight of the composition.
3. The composition of claim 2 wherein a fuel is in the range of
about 50% to about 99% by weight of the composition; the water is
in the range of less than 1% by weight of the composition; the
emulsifier is in the range of about 1% to about 50% by weight of
the composition; and the surfactant in the range of about 0.001% to
about 15% by weight of the composition.
4. The composition of claim 1 wherein the fuel is a diesel
fuel.
5. The composition of claim 1 wherein the water in oil composition
is an emulsified water blended fuel and wherein the fuel is
selected from the group consisting of petroleum distillate fuel
such as diesel, gasoline, fuel oil a mixture thereof; a fuel
derived from vegetables, corn, alfalfa, rapeseed, soybeans, shale,
coal or mixtures thereof; a biodegradable fuel; biodiesel; residual
fuel; bitumen; alcohol; ether; ethanol; Fischer-Tropsch fuels; and
combinations thereof.
6. The composition of claim 1 wherein the surfactant has a low
molecular weight in the range of about 900 g/mol to about 30
g/mol.
7. The composition of claim 1 wherein the surfactant has a low
molecular weight in the range of about 400 g/mol to about 90
g/mol.
8. The composition of claim 1 wherein the surfactant is in the
range of about 0.01% to about 10% by weight of the water in oil
composition.
9. The composition of claim 1 wherein the natural fat surfactant is
selected from the group consisting of triglycerides, hydrolyzed
triglycerides, oxidized products of triglycerides, vegetable oils,
refined vegetable oils, used vegetable oils and combinations
thereof.
10. The composition of claim 1 wherein the non ionic and ionic
surfactants are selected from the group consisting of alkyl
ethoxylates, ethoxylated alkylphenols, alkyl glucosides,
ethoxylated alcohols, ethoxylated amines, ethoxylatedamides amides
derived from fatty acids, amides derived from fatty alcohols,
ethers alcohols, fatty alcohols, esters of fatty acids ethers of
fatty acides, esters of fatty alcohols and combinations
thereof.
11. The composition of claim 1 wherein the non-ionic and ionic
surfactants have a hydrophilic lipophilic balance (HLB) in the
range of about 2 to about 40.
12. The composition of claim 11 wherein the non-ionic and ionic
surfactants are selected from the group consisting of
alkanolamides, alkylarylsulfonates, amine oxides, poly(oxyalkylene)
compounds, including block copolymers comprising alkylene oxide
repeat units (Pluronic.TM.), carboxylated alcohol ethoxylates, such
as fatty esters, glycerol esters, glycol esters, imidazoline
derivatives, lecithin and derivatives, lignin and derivatives,
monoglycerides and diglycerides and derivatives, phosphate esters
and derivatives, propoxylated fatty acids, propoxylated fatty
alcohols, alkyl phenols, sorbitan derivatives, sucrose esters,
derivatives of sucrose esters, sulfates or alcohols or ethoxylated
alcohols or fatty esters, sulfonates of dodecyl aoxtridecyl
benzenes or condensed naphthalenes, and combinations thereof.
13. The composition of claim 8 wherein the non-ionic and ionic
surfactants are selected from the group consisting of C12-C14
alcohol with two ethoxylates, ethomeen C12, Neodol 25-3, oleylic
alcohol with 5 ethoxylates, (nonylphenoxypoly(ethyleneoxy) ethanol,
nonoxynol-8),
(a-(4-nonylphenyl)-.infin.-hydroxypoly(oxy-1,2-ethanediyl), alcohol
ethoxylates, sorbitan monooleate, sorbitan monoisostearate,
glycerol dioleate, glycerol monooleate, lauric acid, myristic acid,
coconut acid, coconut oil, oleic acid, tall oil fatty acid,
linoleic acid, soybean oil, apricot kernel oil, wheat germ oil,
monocarboxylic fatty acids, triglycerides, and combinations
thereof.
14. The composition of claim 1 wherein the co-surfactant is
selected from the group consisting of alcohols, amines, amides,
ketones, esters, ethers and combinations thereof and further
wherein the co-surfactant has from about 1 to about 24 carbon
atoms.
15. The composition of claim 14 wherein the alcohols are selected
from the group consisting of propylene glycol, ethylene glycol,
isopropanol, 2 ethyl hexanol, stearyl alcohol, oleyl alcohol
methanol, ethanol and combinations thereof.
16. The composition of claim 1 wherein the fatty acids and their
amine salt surfactants are selected from the group consisting of
diethyl ethanolamine salts of oleic acid, tall oil fatty acids,
stearic acid, palmitic acid, lauric acid and combinations
thereof.
17. A process for making a water in oil composition comprising
shearing; A) a fuel in the range of about 50% to about 99% by
weight of the composition; B) a water in the range of about 1% to
50% by weight of the composition; C) a high molecular weight
emulsifier in the range of about 1% to about 50% by weight of the
composition; D) a low molecular weight surfactants in the range of
about 0.001% to about 15% by weight of the composition wherein the
surfactant comprises natural fats, non ionic surfactants,
co-surfactant having about 1 to 24 carbon atoms; fatty acids and
their amine salts; and combinations thereof and wherein the
shearing mixing occurs at a shear rate in the range of less than or
equal to 50,000 s.sup.-1; and E) optionally ammonium nitrate.
18. The process of claim 17 wherein the shear rate in the range of
about 20,000 s.sup.-1 to about 1 s.sup.-1.
19. The process of claim 17 wherein the shear rate is in the range
of about 1,000 s.sup.-1 to about 1 s.sup.-1.
20. The process of claim 17 wherein the water in oil composition is
an emulsified water in fuel and wherein the fuel is selected from
the group consisting of petroleum distillate fuel such as diesel,
gasoline, fuel oil a mixture thereof, a fuel derived from
vegetables, corn, alfalfa, rapeseed, soybeans, shale, coal or
mixtures thereof, a biodegradable fuel, biodiesel, residual fuel,
bitumen, alcohol, ether, ethanol and combinations thereof.
21. The composition of claim 1 wherein the emulsifier is selected
from the group consisting of A) at least one fuel-soluble product
made by reacting at least one hydrocarbyl-substituted carboxylic
acid acylating agent with ammonia or an amine including but not
limited to alkanol amine, hydroxy amine, and the like, the
hydrocarbyl substituent of said acylating agent having about 50 to
about 500 carbon atoms; B) a second acylating agent having at least
one hydrocarbyl substituents of up to about 40 carbon atoms, and
reacting that said acylating agent with ammonia or an amine; C) a
water-soluble compound selected from the group consisting of amine
salts, ammonium salts, azide salt, nitrate ester salt, alkali metal
salts, alkaline earth metal salts or mixtures thereof in
combination with A, B, D, E, F or G; D) the reaction product of
polyacidic polymer with at least one fuel soluble product made by
reacting at least one hydrocarbyl-substituted carboxylic acid
acylating agent with ammonia, an amine, a polyamine, an alkanol
amine or hydroxy amines; E) an amino alkylphenol which is made by
reacting an alkylphenol, an aldehyde and an amine resulting in an
amino alkylphenol; F) nitrogen free emulsifier; or G) the
combination of (A), (B), (C), (D), (E), (F) or combinations
thereof.
22. The composition claim 1 wherein the water in oil composition is
an emulsified fuel used to operate an apparatus selected from the
group consisting of an engine, an open flame burner, and an
internal combustion engines.
23. A process for making a water in oil composition comprising
shearing; A) a fuel in the range of about 50% to about 99% by
weight of the composition; B) a water in the range of less than
about 1% by weight of the composition; C) a high molecular weight
emulsifier in the range of about 1% to about 50% by weight of the
composition; D) a low molecular weight surfactants in the range of
about 0.001% to about 15% by weight of the composition wherein the
surfactant comprises natural fats, non ionic surfactants,
co-surfactant having about 1 to 24 carbon atoms; fatty acids and
their amine salts; and combinations thereof and wherein the
shearing mixing occurs at a shear rate in the range of less than or
equal to 50,000 s.sup.-1; and E) optionally ammonium nitrate.
24. The process of claim 23 wherein the water is in the range of
about 0.01% to about 1% by weight of the composition.
25. A process for making a water in oil composition comprising
shearing; A) a fuel in the range of about 50% to about 99% by
weight of the composition; B) a water in the range of less than
about 1% by weight of the composition; C) a high molecular weight
emulsifier in the range of about 1% to about 50% by weight of the
composition; and D) a low molecular weight surfactants in the range
of about 0.001% to about 15% by weight of the composition wherein
the surfactant comprises natural fats, non ionic surfactants,
co-surfactant having about 1 to 24 carbon atoms; fatty acids and
their amine salts; and combinations thereof and wherein the
shearing mixing occurs at a shear rate in the range of less than or
equal to 50,000 s.sup.-1.
26. The process of claim 25 wherein the water is in the range of
about 0.01% to about 1% by weight of the composition.
Description
FIELD OF INVENTION
[0001] The invention relates to a novel low energy process to
produce a water in oil emulsion, in particular water blended fuels
with good emulsion stability. More particularly, the invention
relates to the use of a low molecular weight surfactant to make a
water in oil emulsion by a low energy, low shear process.
BACKGROUND OF THE INVENTION
[0002] Internal combustion engines, especially diesel engines,
using water fuel blends results in the combustion chamber producing
lower nitrogen oxides (NO.sub.x), hydrocarbons and particulate
matter emissions. NO.sub.x emissions have become an important
environmental issue because it contributes to smog and air
pollution. Governmental regulations and environmental concerns have
driven the need to reduce NO.sub.x emissions from engines. In
particular, the U.S. Clean Air Act will require about 90% to 95%
reduction of the current level of internal combustion engines
emissions by the year 2007. Similar regulations are expected in
Europe and other parts of the industrialized world.
[0003] Diesel fueled engines produce NO.sub.x due to the relatively
high flame temperatures reached during combustion. The reduction of
NO.sub.x production conventionally includes the use of catalytic
converters, using "clean" fuels, recirculation of exhaust and
engine timing changes. These methods are typically expensive or
complicated to be readily commercially available. Water is inert
toward combustion, but lowers the peak combustion temperature
resulting in reduced particulates and NO.sub.x formation. When
water is added to the fuel it forms an emulsion and these emulsions
are generally unstable. Stable water in fuel emulsions of a small
particle size are difficult to reach and maintain.
[0004] The use of emulsified fuels to reduce emissions have been
disclosed in other patents and patent applications of Applicant,
such as U.S. Pat. Nos. 6,280,485, 6,383,237, 6,368,367, 6,368,366
and 6,280,485 and U.S. Ser. No. 09/761,482 all incorporated herein
by reference and assigned to the assignee of the present
application. Emulsified fuels have been made by high energy
intensive processes. It would be advantageous to develop a low
energy process to make stable water in fuel emulsions.
[0005] The present invention has discovered the use of certain low
molecular weight surfactants that lower interfacial tension at the
water oil interface resulting in a low energy process to make a
water in oil emulsion fuels.
[0006] The term "NO.sub.x" is used herein to refer to any of the
nitrogen oxides, NO, NO.sub.2, N.sub.2O, or mixtures of two or more
thereof. The terms "water-in-oil" emulsion, "water emulsion",
"emulsions", "water blended fuel", "emulsified water fuel" and
other variations are interchangeable.
SUMMARY OF THE INVENTION
[0007] The invention relates to an emulsified water in oil
composition comprising:
[0008] A. a fuel in the range of about 50% to about 99% by weight
of the composition;
[0009] B. a water in the range of about 1% to about 50% by weight
of the composition;
[0010] C. an emulsifier in the range of about 1% to about 50% by
weight of the composition;
[0011] D. a low molecular weight surfactant in the range of about
0.001% to about 15% by weight of the composition wherein the
surfactant comprises:
[0012] i) natural fats;
[0013] ii) non-ionic and ionic surfactants;
[0014] iii) co-surfactants;
[0015] iv) fatty acids and their amine salts; or
[0016] v) combinations thereof; and
[0017] E. optionally ammonium nitrate.
[0018] The surfactant lowers the interfacial tension of the water
in oil interface during emulsion and formation and is a low
molecular weight surfactant that is less than or equal to 950
g/mol.
[0019] Further, the invention relates to a low energy process for
making a water in oil emulsion comprising emulsifying a fuel, a
water, an emulsifier, and a low molecular weight surfactant. The
water in oil emulsion is produced utilizing a low energy processing
technology using low shear rates and does not need to employ high
shear rates.
[0020] The invention further relates to a low energy process to
produce an emulsified water in oil composition from a concentrate
comprising emulsifying a portion of a fuel, a portion to
substantially all of a water depending on whether it is an
emulsified concentrate or an additive concentrate, substantially
all of an emulsifier, substantially all of a low molecular weight
surfactant to form a concentrate emulsion; and then diluting the
concentrated emulsion with the remaining portion of fuel and water
at the time of use.
[0021] The water in oil emulsion provides good emulsion stability.
The water in oil composition is useful as a fuel for stationary
and/or combustion engines and/or open flame burning apparatus.
DETAILED DESCRIPTION
[0022] The invention discloses a stable emulsified water in oil
composition made by a low energy process by low shearing the
emulsion. The emulsified water in oil composition employs a low
molecular weight surfactant so that a low shear rate mixing
condition can be used to make the emulsion.
[0023] Surfactant
[0024] The surfactant is a small surfactant, having a molecular
weight (Mw) of about less than or equal to about 950 g/mol, in
another embodiment about 900 g/mol to about 30 g/mol, in another
embodiment about 400 g/mol to about 90 g/mol, and in another
embodiment about 350 g/mol to about 150 g/mol. Further the low
molecular weight surfactant has properties to lower the interfacial
tension at the water/oil interface during emulsion formation. The
low molecular weight surfactant further orients itself to the
water/oil interface quickly by populating the water oil interface.
The use of the low molecular weight surfactant results in a low
energy process to make the water in oil emulsion, in particular an
emulsified water fuel.
[0025] The surfactant includes but is not limited to a) natural
fats; b) non-ionics surfactants; c) co-surfactants; d) fatty acids
and their amine salts; and e) combinations thereof. The surfactant
is in the range of about 0.001% to about 15%, in another embodiment
about 0.01% to about 10%, in another embodiment about 0.05% to
about 5%, and in another embodiment about 0.1% to about 3% by
weight of the water in oil composition. The surfactants can be used
alone or in combination. In one embodiment the preferred surfactant
is a natural fat surfactant.
[0026] The natural fat surfactants include but are not limited to
triglycerides, hydrolyzed triglycerides, oxidized products of
triglycerides, vegetable oils, refined vegetable oils, used
vegetable oils and the like. The preferred natural fat surfactant
is a refined used vegetable oil. The natural fats can be used alone
or in combination.
[0027] The non ionic and ionic surfactants include but are not
limited to alkyl ethoxylates, ethoxylated alkylphenols, alkyl
glucosides, ethoxylated alcohols, ethoxylated amines, amides
derived from fatty acids and/or alcohols, ethers or fatty alcohols,
esters of fatty acids and the like. In addition the non-ionic and
ionic surfactants have a hydrophilic lipohilic balance (HLB) in the
range of about 2 to about 40, in one embodiment, about 2 to about
10, in one embodiment about 10 to about 15 and in another
embodiment about 4 to about 8. Examples of these non-ionic and
ionic surfactants are disclosed in McCutcheon's Emulsifiers and
Detergents, 1993, North American & International Edition. Some
examples include but are not limited to alkanolamides,
alkylarylsulfonates, amine oxides, poly(oxyalkylene) compounds,
including block copolymers comprising alkylene oxide repeat units
(e.g., Pluronic.TM. s), carboxylated alcohol ethoxylates,
ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated amines
and amides, ethoxylated fatty acids, ethoxylated fatty esters and
oils, fatty esters, glycerol esters, glycol esters, imidazoline
derivatives, lecithin and derivatives, lignin and derivatives,
monoglycerides, diglycerides and derivatives, phosphate esters and
derivatives, propoxylated and ethoxylated fatty acids or alcohols
or alkyl phenols, sorbitan derivatives, sucrose esters and
derivatives, sulfates or alcohols or ethoxylated alcohols,
sulfonates of dodecyl and tridecyl benzenes or condensed
naphthalenes or petroleum and the like. Preferably the non ionic
surfactants are Neodol 25-3, C12-C14 alcohol with two ethoxylates
and Ethomeen C12. The non ionic and ionic surfactants may be used
alone or in combination.
[0028] Additionally, the ethoxylated alcohols include but are not
limited to oleyl alcohol with 5 ethoxylates, Tomadol 91-8
(purchased from Tomah Chemical) and the like. The ethoxylated
alcohol contains about 5 to about 24, preferably about 8 to about
20 and more preferably about 5 to about 12 carbon atoms with about
3 to about 30 preferably about 5 to about 25 and more preferably
about 5 to about 10 ethylene oxide groups. Preferably the
ethoxylated alcohol is oleyl alcohol with 5 ethoxylates. The
ethoxylated alcohols may be used alone or in combination.
[0029] Another example of non-ionic and ionic surfactants include
but are not limited to IGEPAL CO-630,
(nonylphenoxypoly(ethyleneoxy) ethanol; nonoxynol-8), IGEPAL
CO-430, IGEPAL CO 530, available from Rhone-Poulenc, Cranbury,
N.J., USA; TERGITOL.RTM. NP-9 (a-(4-nonylphenyl)-.infin.-hydrox-
ypoly(oxy-1,2-ethanediyl), available from Union Carbide
Corporation, Danbury, Conn., USA); and alcohol ethoxylates
available from Tomah Products, Inc. under the name "Tomadol".TM.
alcohol ethoxylates and the like.
[0030] In another embodiment the non-ionic and ionic surfactants
include but are not limited to sorbitan esters of fatty acids,
sorbitan monooleate (SMO); sorbitan monoisostearate (SMIS);
glycerol esters like glycerol monooleate (GMO); glycerol dioleate;
and mono-unsaturated acids such as oleic and elaidic acid;
poly-unsaturated acids such as linoleic and linolenic acid;
1,6-dilauryl diglycerol; monoleyl diglycerol; mono cetyl ether of
glycerol; mono oleyl glycerol; diethylene glycol mono-stearate; and
the like. In one embodiment the preferred non-ionic surfactants are
glycerol monooleate, sorbitan monooleate and combinations
thereof.
[0031] In another embodiment the non-ionic and ionic surfactants
include but are not limited to esters of the fatty acids include
but are not limited to glyceryl mono-oleate, glyceryl monostearate,
glyceryl monoricinolaeate, pentaerythritol monolaurate,
pentaerythritol mono and dioleate, pentaerythritol monocaprylate,
mono, di, and triethylene glycol mono-oleate, propylene glycol
monoricinoleate; monoethylene glycol mono-oleate, triethylene
glycol monostearate, sorbitol monolaurate, mannitol mono-oleate,
mannitol dioleate, sorbitol, dioleate, sorbitan dioleate, sorbitan
mono and dilaurate, mannitan mono and distearate, mannitan mono and
dioleate, sorbitan mono and dipalmitate, sorbitan sesquioleate,
mannitan monolaurate, and the like.
[0032] Partial esters obtained from polyhydric alcohols are useful
as the surfactant include but are not limited to the cyclic
ether-alcohol esters which have been modified by being further
reaction with an alkylene oxide or a polyalkyene oxide. For
example, a sorbitan mono-oleate may be further modified by
treatment with ethylene oxide to form the hydroxylether or sorbitan
mono-oleate. Other modified esters of this type may be the
polyoxyalklene sorbitan monostearate, polyoxyalkylene sorbitan
mono-oleate, polyoxyalkylene sorbitan monolaurate, polyoxyalkylene
sorbiitan di and tri-oleate, oleic ester of polyoxyalkylene
mannitol, and the like. In another embodiment the non-ionic
surfactants include but are not limited to the etherification of
the cyclic ether-alcohols of fatty acids containing 12 or more
carbon atoms and may be derived from natural fats and oils or pure
fatty acids or their mixtures may be used. The free fatty acids may
be exemplified by capric, palmitic, oleic, stearic acid or the
like. In addition to the fatty acids other acids may be used and
may be exemplified by naphthenic, sulfonic, salicylic acids and the
like.
[0033] In another embodiment the non-ionic and ionic surfactants
include but are not limited to fatty acid alkanol amides such as
available from Witco Corporation under the name SCHERCOMID.TM.,
SCHERCOMIDT.TM.SO-A and Oleamide DEA, lauric acid, myristic acid,
coconut acid, coconut oil, oleic acid, tall oil fatty acid,
linoleic acid, soybean oil, apricot kernel oil, wheat germ oil,
monocarboxylic fatty acids, triglycerides, and mixtures
thereof.
[0034] The co-surfactant has sufficient polar groups to render the
co-surfactant partially soluble in both phases. The co-surfactants
include but are no limited to alcohols, amines, amides, esters,
ketones, ethers and mixtures thereof. The co-surfactant has at
least 1 to about 24, in another embodiment about 1 to about 10, in
another embodiment about 1 to about 8 carbon atoms. The
co-surfactants may be used alone or in combination.
[0035] The alcohol co-surfactant has about 1 to about 6, in another
embodiment about 1 to about 4 and in another embodiment 1 to 3
hydroxy groups in the molecule. Such alcohols may be aliphatic,
saturated or unsaturated, and straight chain or branched or cyclic
derivatives thereof. Saturated, aliphatic, straight chain alcohols
are preferred. The alcohol surfactants include but are not limited
to propylene glycol, ethylene glycol, isopropanol, 2 ethyl hexanol,
stearyl alcohol, oleyl alcohol, methanol, ethanol and the like. The
preferred alcohol surfactant is propylene glycol. The alcohols may
be used alone or in combinations.
[0036] The fatty acids and their amine salts include but are not
limited to N,N-diethy ethanolamine salts of oleic acid, tall oil
fatty acids, stearic acid, palmitic acid, lauric acid and the like.
The preferable fatty acid and their amine salt is oleic
acid-diethyl ethanol amine salt. The fatty acids and their amine
salts can be used alone or in combination.
[0037] The water in oil emulsion is comprised of a continuous
fuel-phase, a discontinuous water or aqueous phase, an emulsifying
amount of emulsifier and a low molecular weight surfactant so that
the process does not require high speed shear to emulsify the fuel
and water.
[0038] In the practice of the present invention the water in oil
emulsion is made by a batch, semi-batch or a continuous process. A
concentrate may be made and used. The process is capable of
monitoring and adjusting the flow rates of the fuel, emulsifier,
surfactant, additives and/or water to form a stable emulsion with
the desired water droplet size. The water phase of the emulsified
fuel is comprised of droplets having a mean diameter of about 1.0
microns or less, in another embodiment about 0.8 microns or less,
in another embodiment about 0.5 microns or less, in another
embodiment about 0.15 microns or more, in another embodiment about
1.0 micron to about 0.5 microns, and in another embodiment about
1.0 micron to about 0.2 microns.
[0039] The emulsified fuel may be prepared by the steps of mixing
the fuel, the emulsifier, the low molecular weight surfactant, and
other oil soluble additive using low shear techniques to form the
fuel additive mixture. Then the fuel additive mixture is mixed with
water and optionally any desired water soluble additives to form
the desired emulsified water blended fuel.
[0040] In a batch process the water, the emulsifier, the
surfactant, the fuel and optional additives are added to a tank, in
the desired amounts. The mixture is emulsified using an
emulsification device in the vessel, or alternatively the mixture
flows from the vessel via a circular line to the emulsification
device which is external to the vessel, for about 1 to about 20
tank turnovers. The temperature in the range of about ambient
temperature to about 212.degree. F., and in another embodiment in
the range of about 40.degree. F. to about 150.degree. F., and at a
pressure in the range of about atmospheric pressure to about 10
atmospheres, in another embodiment about atmospheric pressure to
about 80 psi, in another embodiment in the range of about 15 psi to
about 30 psi.
[0041] The continuous process described herein depicts another
embodiment of the invention. The feeds of the fuel, emulsifier,
surfactant, water and optional additives are introduced as discrete
feeds or in the alternative combinations of the discreet feeds. The
processing streams are introduced in or as close to the inlet of
the emulsification device as possible. It is preferable that the
emulsifier is added to the fuel as a fuel emulsifier stream prior
to the discreet feeds combining together. The continuous process
generally occurs under ambient conditions. The continuous process
is generally done at atmospheric pressure to about 500 psi, in
another embodiment in the range of about atmospheric pressure to
about 120 psi, and in another embodiment in the range of about
atmospheric pressure to about 50 psi. The continuous process
generally occurs at ambient temperature. In one embodiment the
temperature is in the range of about ambient temperature to about
212.degree. F., and in another embodiment in the range of about
40.degree. F. to about 150.degree. F.
[0042] Alternatively, a concentrate is formed and all or
substantially all the water, and water soluble additive and a
portion of the fuel and all or substantially all the emulsifier and
low molecular weight surfactant is emulsified under low shear
conditions to form a concentrate fuel. The emulsified fuel, when
used, is then blended under normal mixing conditions with the
remaining portion remaining portion of the fuel so that high speed
emulsification conditions are not necessary.
[0043] The process may be in the form of a containerized equipment
unit that operates automatically. The process can be programmed and
monitored locally at the site of its installation, or it can be
programmed and monitored from a location remote from the site of
its installation. The fully formulated water fuel blend is
optionally dispensed to end users at the installation site, or in
another embodiment end users can blend the concentrated emulsion
with the final portion of fuel. This provides a way to make the
water in fuel emulsions available to end users in wide distribution
networks.
[0044] The emulsification may occur at high shear conditions that
are greater than 50,000 s.sup.-1. However, the composition is
emulsified at low shear process conditions. The emulsification
provides for the desired particle size and a uniform dispersion of
water in the fuel and occurs at a shear rate in the range of less
than or equal to 50,000 s.sup.-1, and in another embodiment about
50,000 s.sup.-1 to about 20,000 s.sup.-1, and in another embodiment
of about 20,000 s.sup.-1 to about 1,000 s.sup.-1, and in another
embodiment less than 1,000 s.sup.-1 to about 1 s.sup.-1, and in
another embodiment less than 100 s.sup.-1 to about less than 1
s.sup.-1 and in another embodiment less than 10 s.sup.-1 to about
less than 1 s.sup.-1 shearing. If more than one emulsification step
is used, the shear rates of the emulsification steps can be the
same, similar or different, depending on the emulsifier and low
molecular weight surfactant used.
[0045] The emulsification occurs by any low shear method used in
the industry including but not limited to mixing, mechanical mixer
agitation, static mixers, centrifugal pumps, positive displacement
pumps, orifice plates, and the like. Examples of the devices
include but are not limited to an Aquashear, pipeline static
mixers, rotor/stator mixers and the like. The Aquashear is a
low-pressure hydraulic shear device. The Aquashear mixers are
available from Flow Process Technologies Inc.
[0046] The emulsification is able to occur at a low shear rate and
does not require a high shear rate. By using a low shear rate, low
energy process to make a stable and good emulsified water in oil
blend/fuel one uses less complex or simpler technology, equipment,
devices and is more cost and/or time efficient.
EXAMPLE 1
[0047] About 0.3 parts by weight of glycerol monooleate and about
2.3 parts by weight of a concentrate mixture containing about 23%
wt 2300 MW PIB succinic acid/diethyl ethanolamine salt plus about
31% wt oleic acid/diethyl ethanol amine salt plus about 9.7% of
about a 50% ammonium nitrate solution and about 4.7% propylene
glycol is mixed into about 77.0 parts by weight of diesel fuel.
This organic mixture is then co-fed with about 20 parts by weight
water through an 8.0 mm diameter Sulzer SMX static mixer unit
consisting of about 48 mixing elements at a total volumetric flow
rate of about 470 millilitres per minute. The final white emulsion
was placed in storage bottles. After standing for one month at room
temperature, about 99% of the material was still an emulsion. No
banding or water was observed and only about 1% of the diesel fuel
had separated. Particle size, oil separation, and sedimentation
were found to be comparable to emulsifiers made using high shear
mixing. The particle size of the emulsion was found to have a mean
volume diameter of less than about 1 micron. The storage bottles
were stored at room temperature and observed at various time
intervals. It was observed that the emulsion exhibited stability
behavior equivalent to emulsions made using high shear conditions,
i.e. about 3 part by volume (pbv) of banded material at the bottom
of the storage bottle after 7 days and about 7 pbv after 28 days.
In addition no free water was observed.
[0048] Fuel
[0049] The fuel comprises hydrocarbonaceous petroleum distillate
fuel, non-hydrocarbonaceous materials that include but are not
limited to water, oils, liquid fuels derived from vegetable
sources, liquid fuels derived from minerals and mixtures thereof.
Suitable fuels include, but are not limited to, gasoline, diesel,
kerosene, naphtha, aliphatics and paraffin. The fuel comprises
non-hydrocarbonaceous materials include but is not limited to
alcohols such as methanol, ethanol and the like, ethers such as
diethyl ether, methyl ethyl ether and the like, organo-nitro
compounds and the like; fuels derived from vegetable or mineral
sources such as corn, alfalfa, shale, coal and the like. The fuel
also includes but is not limited to gas to liquid fuels. The fuel
also includes but is not limited to mixtures of one or more
hydrocarbonaceous fuels and one or more non-hydrocarbonaceous
materials. Examples of such mixtures are combinations of gasoline
and ethanol and of diesel fuel and ether and the like.
[0050] In one embodiment, the fuel is any gasoline. Including, but
not limited to a chlorine-free gasoline or a low-chlorine gasoline,
or a low sulfur gasoline or sulfur-free gasoline and the like.
[0051] In one embodiment, the fuel is any diesel fuel. The diesel
fuels include, but are not limited to, those that contain alcohols
and esters, has a sulfur content of up to about 0.05% by weight or
sulfur-free, is a chlorine-free or low-chlorine diesel fuel and the
like.
[0052] The fuel is present in the emulsified fuel at a
concentration of about 50% to about 95% by weight, and in one
embodiment about 60% to about 95% by weight, and in one embodiment
about 65% to about 85% by weight, and in one embodiment about 80%
to about 90% by weight of the emulsified fuel.
[0053] Water
[0054] The water used in the emulsified fuel may be taken from any
source. The water includes but is not limited to tap, deionized,
demineralized, purified, for example, using reverse osmosis or
distillation, and the like. The water includes water mixtures that
further includes but are not limited to antifreeze components such
as alcohols and glycols, ammonium salts such as ammonium nitrate,
ammonium maleate, ammonium acetate and the like, and combinations
thereof; and other water soluble additives.
[0055] The water is present in the emulsified fuel at a
concentration of about 1% to about 50% by weight, in one embodiment
about 5% to about 40% being weight, in one embodiment about 5% to
about 25% by weight, and in one embodiment about 10% to about 20%
by weight of the emulsified fuel.
[0056] In another embodiment the water is present in the emulsified
fuel at a concentration of less than 1% by weight, in another
embodiment less than 0.5% by weight, in another embodiment less
than 0.1% by weight, and in another embodiment in the range of
about 0.1% to about 1% by weight of the emulsified fuel. An
emulsified water in oil composition can be made with water at these
low levels with the fuel, the emulsifier, the surfactant and
optionally ammonium nitrate and in another embodiment without the
surfactant and with the fuel, the emulsifier and optionally the
ammonium nitrate.
[0057] Emulsifier
[0058] The emulsifier includes but is not limited to
[0059] (i) at least one fuel-soluble product made by reacting at
least one hydrocarbyl-substituted carboxylic acid acylating agent
with ammonia or an amine including but not limited to alkanol
amine, hydroxy amine, and the like, the hydrocarbyl substituent of
said acylating agent having about 50 to about 500 carbon atoms;
[0060] (ii) a second acylating agent having at least one
hydrocarbyl substituents of up to about 40 carbon atoms, and
reacting that said acylating agent with ammonia or an amine;
[0061] (iii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0062] (iv) mixture of (ii) or (iii) with (i) or a mixture of (i),
(ii), and (iii);
[0063] (v) a water-soluble compound selected from the group
consisting of amine salts, ammonium salts, azide compounds, nitrate
esters, nitramine, nitrocompounds, alkali metal salts, alkaline
earth metal salts, in combination with (i), (ii), (iii), (v), (vii)
or combinations thereof;
[0064] (vi) the reaction product of polyacidic polymer with at
least one fuel soluble product made by reacting at least one
hydrocarbyl-substituted carboxylic acid acylating agent with
ammonia, an amine, a polyamine, an alkanol amine or hydroxy
amines;
[0065] (vii) an amino alkylphenol which is made by reacting an
alkylphenol, an aldehyde and an amine resulting in an amino
alkylphenol;
[0066] (viii) a nitrogen free emulsifier; or
[0067] (ix) the combination of (i) through (viii) or combinations
thereof.
[0068] The emulsifier has at least one high molecular weight
component. The emulsifier has a high molecular weight component
relative to the surfactant which has a low molecular weight.
[0069] The fuel-soluble product (i) of the emulsifier may be at
least one fuel-soluble product made by reacting at least one
hydrocarbyl-substituted carboxylic acid acylating agent with
ammonia or an amine including but not limited to alkanol amines,
hydroxy amines, and the like, the hydrocarbyl substituent of said
acylating agent having about 50 to about 500 carbon atoms, and is
described in greater detail in U.S. Ser. No. 09/761,482, An
Emulsifier For An Aqueous Hydrocarbon Fuel, incorporated by
reference herein.
[0070] The hydrocarbyl-substituted carboxylic acid acylating agents
may be carboxylic acids or reactive equivalents of such acids. The
reactive equivalents may be acid halides, anhydrides, or esters,
including partial esters and the like. The hydrocarbyl substituents
for these carboxylic acid acylating agents may contain from about
50 to about 500 carbon atoms, and in one embodiment about 50 to
about 300 carbon atoms, and in one embodiment about 60 to about 200
carbon atoms. In one embodiment, the hydrocarbyl substituents of
these acylating agents have number average molecular weights of
about 700 to about 3000, and in one embodiment about 900 to about
2300.
[0071] In another embodiment, the fuel soluble product (i) of the
present invention comprises an emulsifying amount of at least one
of a fuel-soluble hydrocarbyl-substituted carboxylic acylating
agent and a reaction product of said acylating agent with at least
one of ammonia, an amine, an alcohol, a reactive metal, a reactive
metal compound or a mixture of two or more thereof, wherein the
hydrocarbyl substituent comprises a group derived from at least one
polyolefin, said polyolefin having {overscore (M)}.sub.w/{overscore
(M)}.sub.n greater than about 5.
[0072] The hydrocarbyl substituted acylating agents have a
hydrocarbyl group substituent that is derived from a polyolefin,
with polydispersity and other features as described below.
Generally, it has a number average molecular weight of at least
600, 700, or 800, to 5000 or more, often up to 3000, 2500, 1600,
1300, or 1200. Typically, less than 5% by weight of the polyolefin
molecules have {overscore (M)}.sub.n less than about 250, more
often the polyolefin has {overscore (M)}.sub.n of at least about
800. The polyolefin preferably contains at least about 30% terminal
vinylidene groups, more often at least about 60% and more
preferably at least about 75% or about 85% terminal vinylidene
groups. The polyolefin has polydispersity, {overscore
(M)}.sub.w/{overscore (M)}.sub.n, greater than about 5, more often
from about 6 to about 20. The hydrocarbyl group is typically
derived from a polyolefin or a polymerizable derivative thereof,
including homopolymers and interpolymers of olefin monomers having
2 to 30, to 6, or to 4 carbon atoms, and mixtures thereof. In a
preferred embodiment the polyolefin is polyisobutenyl.
[0073] Suitable olefin polymer hydrocarbyl groups, having suitable
polydispersity, can be prepared by heteropolyacid catalyzed
polymerization of olefins under conventional conditions. Preferred
heteroplyacids include a phosphotungstic acid, a phosphomolybidc
acid, a silicotungstic acid, a silicomolybdic acid and the
like.
[0074] The hydrocarbyl-substituted carboxylic acid acylating agents
may be made by reacting one or more alpha-beta olefinically
unsaturated carboxylic acid reagents containing 2 to about 20
carbon atoms, exclusive of the carboxyl groups, with one or more
olefin polymers as described more fully hereinafter. This reaction
may occur under the conditions to add the alpha-beta olefinically
unsaturated carboxylic acid reagents via a free radical addition
process.
[0075] In one embodiment, the hydrocarbyl-substituted carboxylic
acid acylating agent is a polyisobutene-substituted succinic
anhydride, the polyisobutene substituent having a number average
molecular weight of about 1,500 to about 3,000, in one embodiment
about 1,800 to about 2,300, in one embodiment about 700 to about
1300, in one embodiment about 800 to about 1000, said first
polyisobutene-substituted succinic anhydride being characterized by
about 1.3 to about 2.5, and in one embodiment about 1.7 to about
2.1 In one embodiment, the hydrocarbyl-substituted carboxylic acid
acylating agent is a polyisobutene-substituted succinic anhydride,
the polyisobutene substituent having a number average molecular
weight of about 1,500 to about 3,000, and in one embodiment about
1,800 to about 2,300, said first polyisobutene-substituted succinic
anhydride being characterized by about 1.3 to about 2.5, and in one
embodiment about 1.7 to about 2.1, in one embodiment about 1.0 to
about 1.3, and in one embodiment about 1.0 to about 1.2 succinic
groups per equivalent weight of the polyisobutene substituent.
[0076] The fuel-soluble product (i) may be formed using ammonia, an
amine and/or the metal bases of metals such as Na, K, Ca, and the
like. The amines useful for reacting with the acylating agent to
form the product (i) including but are not limited to, monoamines,
polyamines, alkanol amines, hydroxy amines, and mixtures thereof,
and amines may be primary, secondary or tertiary amines.
[0077] Examples of primary and secondary monoamines include
ethylamine, diethylamine, n-butylamine, di-n-butylamine,
allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,
methyllaurylamine, oleylamine, N-methyloctylamine, dodecylamine,
and octadecylamine. Suitable examples of tertiary monoamines
include trimethylamine, triethylamine, tripropylamine,
tributylamine, monoethyldimethylamine, dimethylpropylamine,
dimethylbutylamine, dimethylpentylamine, dimethylhexylamine,
dimethylheptylamine, and dimethyloctylamine.
[0078] The amines include but are not limited to hydroxyamines,
such as mono-, di-, and triethanolamine, dimethylethanol amine,
diethylethanol amine, di-(3-hydroxy propyl) amine,
N-(3-hydroxybutyl) amine, N-(4-hydroxy butyl) amine, and
N,N-di-(2-hydroxypropyl) amine; alkylene polyamines such as
methylene polyamines, ethylene polyamines, butylene polyamines,
propylene polyamines, pentylene polyamines, and the like. Specific
examples of such polyamines include ethylene diamine, diethylene
triamine, triethylene tetramine, propylene diamine, trimethylene
diamine, tripropylene tetramine, tetraethylene pentamine,
hexaethylene heptamine, pentaethylene hexamine, or a mixture of two
or more thereof; ethylene polyamine bottoms or a heavy polyamine.
The fuel-soluble product (i) may be a salt, an ester, an
ester/salt, an amide, an amide, or a combination of two or more
thereof.
[0079] The fuel-soluble product (i) may be present in the water
fuel emulsion at a concentration of up to about 15% by weight based
on the overall weight of the emulsion, and in one embodiment about
0.1 to about 15% by weight, and an one embodiment about 0.1 to
about 10% by weight, and in one embodiment about 0.1 to about 5% by
weight, and in one embodiment about 0.1 to about 2% by weight, and
in one embodiment about 0.1 to about 1% by weight, and in one
embodiment about 0.1 to about 0.7% by weight.
[0080] The second acylating agent (ii) of this invention includes
carboxylic acids and their reactive equivalents such as acid
halides and anhydrides.
[0081] In one embodiment, the carboxylic acid is a monocarboxylic
acid of about 1 to about 35 carbon atoms, and in one embodiment
about 16 to about 24 carbon atoms. Examples of these monocarboxylic
acids include lauric acid, oleic acid, isostearic acid, palmitic
acid, stearic acid, linoleic acid, arachidic acid, gadoleic acid,
behenic acid, erucic acid, tall oil fatty acids, lignoceric acid
and the like. These acids may be saturated, unsaturated, or have
other functional groups, such as hydroxy groups, as in 12-hydroxy
stearic acid, from the hydrocarbyl backbone.
[0082] In one embodiment, the carboxylic acid is a
hydrocarbyl-substituted succinic acid represented correspondingly
by the formula 1
[0083] wherein formula R is hydrocarbyl group of about 12 to about
35, and in one embodiment from about 12 to about 30, and in one
embodiment from about 16 to about 24 and in one embodiment from
about 26 to about 35 carbon atoms. The production of such
hydrocarbyl-substituted succinic acids or anhydrides via alkylation
of maleic acid or anhydride or its derivatives with a
halohydrocarbon or via reaction of maleic acid or anhydride with an
olefin polymer having a terminal double bond is known to those of
skill in the art.
[0084] In one embodiment, the acylating agent (ii) is a carboxylic
acid or the acylating agent (ii) used to prepare carboxylic acid
and is made by reacting one or more alpha-beta olefinically
unsaturated carboxylic acid reagents containing about 2 to about 20
carbon atoms, exclusive of the carboxyl based groups, with one or
more olefin polymers containing at least about 16 carbon atoms.
[0085] In the one embodiment, the ratio of the first acylating
agent (i), to the second acylating agent (ii) in the emulsified
fuel is in the range of about 9:1 to about 1:9; in another
embodiment in the range of about 5:1 to about 1:5; and in another
embodiment in the range of about 1:3 to about 3.1.
[0086] The ionic or nonionic compound (iii) of the emulsifier has a
hydrophilic-lipophilic balance (HLB, which refers to the size and
strength of the polar (hydrophilic) and non-polar (lipophilic)
groups on the surfactant molecule) in the range of about 1 to about
40, and in one embodiment about 4 to about 15 and is described in
greater detail in U.S. Ser. No. 09/761,482, An Emulsifier For An
Aqueous Hydrocarbon Fuel, incorporated by reference herein.
Examples of these compounds are disclosed in McCutcheon's
Emulsifiers and Detergents, 1998, North American &
International Edition. Pages 1-235 of the North American Edition
and pages 1-199 of the International Edition are incorporated
herein by reference for their disclosure of such ionic and nonionic
compounds having an HLB in the range of about 1 to about 40, in one
embodiment about 1 to about 30, in one embodiment about 1 to 20,
and in another embodiment about 1 to about 10. Examples include low
molecular weight variants of (i) or (vii) such as those having a
hydrocarbon group in the range of C.sub.8 or C.sub.20. Useful
compounds include alkanolamines, carboxylates including amine
salts, metallic salts and the like, alkylarylsulfonates, amine
oxides, poly(oxyalkylene) compounds, including block copolymers
comprising alkylene oxide repeat units, carboxylated alcohol
ethoxylates, ethoxylated alcohols, ethoxylated alkylphenols,
ethoxylated amines and amides, ethoxylated fatty acids, ethoxylated
fatty esters and oils, fatty esters, fatty acid amides, including
but not limited to amides from tall oil fatty acids and polyamides,
glycerol esters, glycol esters, sorbitan esters, imidazoline
derivatives, lecithin and derivatives, lignin and derivatives,
monoglycerides and derivatives, olefin sulfonates, phosphate esters
and derivatives, propoxylated and ethoxylated fatty acids or
alcohols or alkylphenols, sorbitan derivatives, sucrose esters and
derivatives, sulfates or alcohols or ethoxylated alcohols or fatty
esters, sulfonates of dodecyl and tridecyl benzenes or condensed
naphthalenes or petroleum, sulfosuccinates and derivatives, and
tridecyl and dodecyl benzene sulfonic acids.
[0087] The emulsifier (iv) may be a mixture of (i) and (ii)
described above and is further described in detail in U.S. Ser. No.
09/761,482, An Emulsifier For An Aqueous Hydrocarbon Fuel,
incorporated by reference herein.
[0088] The emulsifier of the water-soluble compound (v) may be an
amine salt, ammonium salt, azide compound, nitro compound, nitrate
salts, alkali metal salt, alkaline earth metal salt, or mixtures of
two or more thereof and is described in greater detail in U.S. Ser.
No. 09/761,482, An Emulsifier For An Aqueous Hydrocarbon Fuel,
incorporated by reference herein. These compounds are distinct from
the fuel-soluble product (i) and the ionic or nonionic compound
(ii) discussed above. These water-soluble compounds include organic
amine nitrates, nitrate esters, azides, nitramines and nitro
compounds. Also included are alkali and alkaline earth metal
carbonates, sulfates, sulfides, sulfonates, and the like. In
another embodiment the water soluble compound is in the form of a
salt, such as an amine salt, ammonia salt, azide salt, alkali metal
salt, alkaline earth metal salt, nitrate salt and mixtures
thereof.
[0089] Particularly useful are the amine or ammonium salts such as
ammonium nitrate, ammonium acetate, methylammonium nitrate,
methylammonium acetate, hydroxy ammonium nitrate, ethylene diamine
diacetate; urea nitrate; urea; guanidinium nitrate; and
combinations thereof. However, these ammonium salts of the
emulsifier, if used are independent of and distinct and separate
from the aqueous organic ammonium salt compound of the emulsified
fuel discussed above.
[0090] In one embodiment the emulsifier (vi) is the reaction
product of A) a polyacidic polymer, B) at least one fuel soluble
product made by reacting at least one hydrocarbyl-substituted
carboxylic acid acylating agent, and C) a hydroxy amine and/or a
polyamine and is described in greater detail in U.S. Ser. No.
09/761,482, An Emulsifier For An Aqueous Hydrocarbon Fuel,
incorporated by reference herein.
[0091] The polyacidic polymers used in the reaction include but are
not limited to C.sub.4 to C.sub.30; preferably C.sub.8 to C.sub.20
olefin/maleic anhydride copolymers; maleic anhydride/styrene
copolymers; poly-maleic anhydride; acrylic and methacrylic acid
containing polymers; poly-(alkyl)acrylates; reaction products of
maleic anhydride with polymers with multiple double bonds;
[0092] A copolymer of an olefin and a monomer having the structure:
2
[0093] wherein X and X1 are the same or different provided that at
least one of X and X.sub.1 is such that the copolymer can function
as a carboxylic acylating agent; and combinations therein.
[0094] The emulsifier produced from the reaction product of the
polyacidic polymer with the fuel soluble product (i) comprises
about 25% to about 95% of fuel soluble product and about 0.1% to
about 50% of the polyacidic polymer; preferably about 50% to about
92% fuel soluble product and about 1% to about 20% of the
polyacidic polymer, and most preferably about 70% to about 90% of
fuel soluble product and about 5% to about 10% of the polyacidic
polymer. In one embodiment the emulsifier is described as a
polyalkenyl succinimide crosslinked with an olefin/maleic anhydride
copolymer.
[0095] The amino alkyl emulsifier (vii) is comprised of the
reaction product of an amino alkylphenol, an aldehyde, and an amine
resulting in amino alkylphenol. The amino alkylphenol can be made
by (a) the reaction of alkylphenol directly with an aldehyde and an
amine resulting in an alkylphenol monomer connected by a methylene
group to an amine, (b) the reaction of an alkylphenol with an
aldehyde resulting in an oligomer wherein the alkylphenols are
bridged with methylene groups, the oligomer is then reacted with
more aldehyde and an amine to give a Mannich product, or (c) a
mixture of (a) and (b) and is described in greater detail in U.S.
Ser. No. 09/977,747 entitled A Continuous Process For Making An
Aqueous Hydrocarbon Fuel Emulsion incorporated by reference
herein.
[0096] The alkylphenols have an alkyl group selected from C.sub.1
to C.sub.200, preferably C.sub.6 to C.sub.170 wherein the alkyl
group is either linear, branched or a combination thereof. The
alkylphenols include, but are not limited to, polypropylphenol,
polybutylphenol, poly(isobutenyl)phenol, polyamylphenol,
tetrapropylphenol, similarly substituted phenols and the like. The
preferred alkylphenols are tetrapropenylphenol and
poly(isobutenyl)phenol.
[0097] The aldehydes include, but are not limited to, aliphatic
aldehydes, such as formaldehyde; acetaldehyde; aldol
(.beta.-hydroxy butyraldehyde); aromatic aldehydes, such as
benzaldehyde; heterocyclic aldehydes, such as furfural, and the
like. The aldehyde may contain a substituent group such as
hydroxyl, halogen, nitro and the like; in which the substituent
does not take a major part in the reaction. The preferred aldehyde
is formaldehyde.
[0098] The amines are those which contain an amino group
characterized by the presence of at least one active hydrogen atom.
The amines may be primary amino groups, secondary amino groups, or
combinations of primary and secondary amino groups.
[0099] The amines include, but are not limited to, alkanolamines;
di- and polyamine (polyalkyene amines); polyalkyl polyamines;
propylenediamine, the aromatic amines such as o-, m- and
p-phenylene diamine, diamino naphthalenes; the acid-substituted
polyalkylpolyamines, and the corresponding formyl-, propionyl-,
butyryl-, and the like N-substituted compounds; and the
corresponding cyclized compounds formed therefrom, such as the
N-alkyl amines of imidazolidine and pyrimidine. Substituent groups
attached to the carbon atoms of these amines are typified by alkyl,
aryl, alkaryl, aralkyl, cycloalkyl, and amino compounds. The amino
alkylphenols emulsifier of this invention may be made by reacting
the alkylphenol:aldehyde:amine in a ratio range of 1:1:0.1 molar to
1:2:2 molar, in one embodiment preferably 1:0.9:0.1 to 1:1.9:1.9,
in one embodiment preferably 1:1.5:1.2 molar to 1:1.9:1.8 molar,
and in one embodiment preferably 1:0.8:0.3 to 1:1.5:0.7, resulting
in the amino alkylphenol emulsifier. In another embodiment of this
invention the amino alkylphenol is made by the reaction of an
alkylphenol with an aldehyde, resulting in an oligomer wherein the
alkylphenols are bridged with methylene groups; then the oligomer
is reacted with more aldehyde and amine to give the emulsifier
Mannich product of this invention. The reaction is prepared by any
known method such as an emulsion, a solution, a suspension, and a
continuous addition bulk process. The reaction is carried out under
conditions that provide for the formation of the desired
product.
[0100] The nitrogen-free emulsifier (viii) comprises:
[0101] (viii)(a) a hydrocarbyl substituted carboxylic acid, or a
reaction product of the hydrocarbyl substituted carboxylic acid or
a reactive equivalent of such acid with an alcohol, the hydrocarbyl
substituent of the acid or reactive equivalent thereof containing
at least about 30 carbon atoms; and
[0102] (viii)(b) at least one compound represented by one or more
of the formulae: 3
[0103] wherein each R is independently hydrogen or a hydrocarbyl
group of up to about 60 carbon atoms; each R' and R" is
independently an alkylene group of 1 to about 20 carbon atoms; each
R'" is independently hydrogen, or an acyl or hydrocarbyl group of
up to about 30 carbon atoms; n is a number in the range of zero to
about 50; and x, y and z are independently numbers in the range of
zero to about 50 with the total for x, y and z being at least 1.
This emulsifier is further disclosed in Applicants U.S. application
entitled "Water Blended Fuel Composition", Applicants' reference
number 3134, U.S. Ser. No. ______, incorporated by reference
herein.
[0104] The emulsifier component (viii) (a) may be a hydrocarbyl
substituted carboxylic acid, or a reaction product of the
hydrocarbyl substituted carboxylic acid or a reactive equivalent
thereof with an alcohol. The carboxylic acids may be monobasic or
polybasic. The polybasic acids include dicarboxylic acids, although
tricarboxylic and tetracarboxylic acids may be used. The reactive
equivalents may be acid halides, (e.g., chlorides), anhydrides or
esters, including partial esters, and the like.
[0105] The alcohol which may be reacted with the hydrocarbyl
substituted carboxylic acid or reactive equivalent to form
emulsifier component (iii)(a) may be a mono- or a polyhydric
hydrocarbon-based alcohol such as methanol, ethanol, the propanols,
butanols, pentanols, hexanols, heptanols, octanols, decanols, and
the like. Also included are fatty alcohols and mixtures thereof,
including saturated alcohols such as lauryl, myristyl, cetyl,
stearyl and behenyl alcohols, and unsaturated alcohols such as
palmitoleyl, oleyl and eicosenyl. Higher synthetic monohydric
alcohols of the type formed by the Oxo process (e.g.,
2-ethylhexanol), by the aldol condensation, or by
organoaluminum-catalyze- d oligomerixation of alpha-olefins (e.g.,
ethylene), followed by oxidation, may be used. Alicyclic analogs of
the above-described alcohols may be used; examples include
cyclopentanol, cyclohexanol, cyclododecanol, and the like.
[0106] The polyhydroxy compounds that may be used include ethylene,
propylene, butylene, pentylene, hexylene and heptylene glycols;
tri-, tetra-, penta-, hexa- and heptamethylene glycols and
hydrocarbon-substituted analogs thereof (e.g.,
2-ethyl-1,3-trimethylene glycol, neopentyl glycol, etc.), as well
as polyoxyalkylene compounds such as diethylene and higher
polyethylene glycols, tripropylene glycol, dibutylene glycol,
dipentylene glycol, dihexylene glycol and diheptylene glycol, and
their monoethers. A glycol that may be used is 1,2-propane
diol.
[0107] Phenol, naphthols, substituted phenols (e.g., the cresols),
and dihydroxyaromatic compounds (e.g., resorcinol, hydroquinone),
as well as a benzyl alcohol and similar di-hydroxy compounds
wherein the second hydroxy group is directly bonded to an aromatic
carbon (e.g., 3-HO.phi.CH.sub.2OH wherein .phi. is a divalent
benzene ring) may be used. Sugar alcohols of the general formula
HOCH.sub.2 (CHOH).sub.1-5 CH.sub.2OH such as glycerol, sorbitol,
mannitol, and the like, and their partially esterified derivatives
may be used. Oligomers of such sugar alcohols, including
diglycerol, triglycerol, hexaglycerol, and the like, and their
partially esterfied derivatives may be used. Methylol polyols such
as pentaerythritol and its oligomers (di- and tripentaerythritol,
etc.), trimethylolethane, trimethylolpropane, and the like may be
used.
[0108] The emulsifier component (viii)(a) may be in the form of an
acid, an ester, or a mixture thereof. The acid may be formed by
reacting a hydrocarbyl substituted carboxylic acid reactive
equivalent with water to provide the desired acid. For example,
hydrocarbyl (e.g., polyisobutene) substituted succinic anhydride
may be reacted with water to form hydrocarbyl substituted succinic
acid. The reaction between the hydrocarbyl substituted carboxylic
acid or reactive equivalent thereof and the alcohol to form an
ester may be carried out under suitable ester forming reaction
conditions. In one embodiment, the hydrocarbyl substituted
carboxylic acid or reactive equivalent thereof and the alcohol are
reacted in amounts sufficient to provide from about 0.3 to about 3
equivalents of the acid or reactive equivalent thereof per
equivalent of alcohol. In one embodiment, this ratio is from about
0.5:1 to about 2:1.
[0109] The emulsifier component (viii)(b) may be at least one
compound represented by one or more of the formulae: 4
[0110] wherein each R is independently hydrogen or a hydrocarbyl
group of up to about 60 carbon atoms; each R' and R" is
independently an alkylene group of 1 to about 20 carbon atoms; each
R'" is independently hydrogen, or an acyl or hydrocarbyl group of
up to about 30 carbon atoms; n is a number in the range of zero to
about 50; and x, y and z are independently numbers in the range of
zero to about 50 with the total for x, y and z being at least 1. In
the above formulae, R may be a hydrocarbyl group of about 6 to
about 60 carbon atoms, and in one embodiment abut 6 to about 45
carbon atoms, and in one embodiment about 6 to about 30 carbon
atoms, and in one embodiment about 14 to about 30 carbon atoms. In
one embodiment, R may be a hydrocarbyl group of about 9 to about 11
carbon atoms. R' and R" may be independently alkylene groups of
about 1 to about 6 carbon atoms, and in one embodiment about 1 to
about 4 carbon atoms. In one embodiment, R' is an alkylene group
containing about 2 to about 3 carbon atoms, and in one embodiment
about 2 carbon atoms. In one embodiment, R" is an alkylene group
containing 1 carbon atom. R'" may be an acyl or hydrocarbyl group
of 1 to about 30 carbon atoms, and in one embodiment 1 to about 24
carbon atoms, and in one embodiment 1 to about 18 carbon atoms, and
in one embodiment 1 to about 12 carbon atoms, and in one embodiment
1 to about 6 carbon atoms. n may be a number in the range of 1 to
about 50, and in one embodiment 1 to about 30, and in one
embodiment 1 to about 20, and in one embodiment 1 to about 12, and
in one embodiment about 4 to about 10, and in one embodiment about
5 to about 10, and in one embodiment about 5 to about 8, and in one
embodiment about 5 or about 6. x, y and z may be independently
numbers in the range of zero to about 50, and in one embodiment
zero to about 30, and in one embodiment zero to about 10; with the
total of x, y and z being at least 1, and in one embodiment in the
range of 1 to about 50, and in one embodiment 10 to about 40, and
in one embodiment 20 to about 30, and in one embodiment about
25.
[0111] Examples of compounds represented by formula (viii-b-1) that
may be used include: C.sub.9-C.sub.11 alkoxy poly (ethoxy).sub.8
alcohol; C.sub.12-C.sub.15 alkoxy poly (isopropoxy).sub.22-26
alcohol; oleyl alcohol pentaethoxylate; and the like.
[0112] Examples of compounds represented by formula (viii-b-2) that
may be used include diglycerol monooleate, diglycerol monosteaate,
polyglycerol monooleate, and the like.
[0113] Examples of compounds represented by formula (viii-b-3) that
may be used include polyethylene glycol (Mn=200) distearate,
polyethylene glycol (Mn=400) distearate, polyethylene glycol
(Mn=200) dioleate, polyethylene glycol (Mn=400) soya bean oil
ester, and the like.
[0114] Examples of compounds represented by formula (viii-b-4) that
may be used include glycerol monooleate, diglycerol dioleate,
diglycerol distearate, polyglycerol dioleate, and the like.
[0115] Examples of compounds represented by formula (viii-b-5) that
may be used include sorbitan monooleate, sorbitan monoisostearate,
sorbitan sesquioleate, and sorbitan trioleate, and the like.
[0116] Examples of compounds represented by formula (viii-b-6) that
may be used include polyethoxy glycerol trioleate wherein the
compound contains 25 ethoxy groups.
[0117] In one embodiment, the emulsifier (viii)(b) is an alkoxy
polyethoxy alcohol wherein the alkoxy group contains about 14 to
about 30 carbon atoms and the polyethoxy group contains up to about
10 ethoxy groups, and in one embodiment about 5 to about 10 ethoxy
groups, and in one embodiment about 5 or 6 ethoxy groups.
[0118] In one embodiment, the emulsifier (viii)(b) is an alkoxy
polyethoxy alcohol wherein the alkoxy group contains about 9 to
about 11 carbon atoms and the polyethoxy group contains about 8
ethoxy groups. An optional acid component that may be used in one
embodiment with the nitrogen free emulsifier and in another
embodiment with each of the emulsifiers alone or in combinations
may be used in the inventive fuel composition comprises one or more
acids having a pKa of up to about 6, and in one embodiment up to
about 5, and in one embodiment up to about 4, and in one embodiment
from about 0 to about 4, and in one embodiment about 1 to about
3.5, and in one embodiment about 1.5 to about 3. This acid
component includes but is not limited too carboxylic acid, formic
acid, acetylenedicarboxylic acid, benzenehexacarboxylic acid,
benzenepentacarboxylic acid, benzenetetracarboxylic acid,
benzenetricarboxylic acid, 2-butyn-1,4-dioic acid, 2-butynoic acid,
citraconic acid, cyclopropane-1,1-dicarboxylic acid,
2,6-dihydroxybenzoic acid, dihydroxymaleic acid, dihydroxymalic
acid, dihydroxytatric acid, alpha, alpha-dimethyloxaloacetic acid,
dipropylmalonic acid, ethylene oxide dicarboxylic acid,
hydroxyaspartic acid, maleic acid, 2-oxobutanoic acid,
triethylsuccinic acid, citric acid, tartaric acid, glyoxylic acid,
oxalic acid, lactic acid, oxomalonic acid (mesoxalic acid), and
mixtures thereof.
[0119] When used, this acid component may function as an ionizing
agent. The concentration of this acid component in the water
blended fuel composition may range up to about 5 percent by weight,
and in one embodiment from about 0.001 to about 3 percent by
weight, and in one embodiment about 0.01 to about 1 percent by
weight.
[0120] Other Additives
[0121] In one embodiment, the emulsified fuel contains a cetane
improver. The cetane improvers that are useful include but are not
limited to peroxides, nitrates, nitrites, nitrocarbamates, and the
like. Useful cetane improvers include but are not limited to
nitropropane, dinitropropane, tetranitromethane,
2-nitro-2-methyl-1-butanol, 2-methyl-2-nitro-1-propanol, and the
like. Also included are nitrate esters of substituted or
unsubstituted aliphatic or cycloaliphatic alcohols which may be
monohydric or polyhydric. These include substituted and
unsubstituted alkyl or cycloalkyl nitrates having up to about 10
carbon atoms, and in one embodiment about 2 to about 10 carbon
atoms. The alkyl group may be either linear or branched, or a
mixture of linear or branched alkyl groups. Examples include methyl
nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl
nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate,
isooctyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl
nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl
nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate,
sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, cyclopentyl
nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, and
isopropylcyclohexyl nitrate. Also useful are the nitrate esters of
alkoxy-substituted aliphatic alcohols such as 2-ethoxyethyl
nitrate, 2-(2-ethoxy-ethoxy) ethyl nitrate,
1-methoxypropyl-2-nitrate, 4-ethoxybutyl nitrate, etc., as well as
diol nitrates such as 1,6-hexamethylene dinitrate. A useful cetane
improver is 2-ethylhexyl nitrate.
[0122] The concentration of the cetane improver in the emulsified
fuel is at any concentration sufficient to provide the emulsion
with the desired cetane number. In one embodiment, the
concentration of the cetane improver is at a level of up to about
10% by weight, and in one embodiment about 0.05% to about 10% by
weight, and in one embodiment about 0.05% to about 5% by weight,
and in one embodiment about 0.05% to about 1% by weight of the
emulsified fuel.
[0123] In addition to the foregoing materials, other fuel additives
that known to those skilled in the art may be used in the
emulsified fuel. These include but are not limited to dyes, rust
inhibitors such as alkylated succinic acids and anhydrides,
bacteriostatic agents, gum inhibitors, metal deactivators, upper
cylinder lubricants and the like.
[0124] The total concentration of the additives, in the emulsified
fuel is from about 0.05% to about 30% by weight, and in one
embodiment about 0.1% to about 20% by weight, and in one embodiment
about 0.1% to about 15% by weight, and in one embodiment about 0.1%
to about 10% by weight, and in one embodiment about 0.1% to about
5% by weight of the emulsified fuel.
[0125] The additives, including the foregoing emulsifiers, may be
diluted with a substantially inert, normally liquid organic solvent
such as naphtha, benzene, toluene, xylene or diesel fuel to form an
additive concentrate which is then mixed with the fuel and water to
form the emulsified fuel.
[0126] The emulsified fuel may contain up to about 60% by weight
organic solvent, and in one embodiment about 0.01% to about 50% by
weight, and in one embodiment about 0.01% to about 20% by weight,
and in one embodiment about 0.1% to about 5% by weight, and in one
embodiment about 0.1% to about 3% by weight of the emulsified
fuel.
[0127] The emulsified fuel may additionally contain an antifreeze
agent. The antifreeze agent is typically an alcohol. Examples
include but are not limited to ethylene glycol, propylene glycol,
methanol, ethanol, glycerol and mixtures of two or more thereof.
The antifreeze agent is typically used at a concentration
sufficient to prevent freezing of the water used in the water fuel
emulsion. The concentration is therefore dependent upon the
temperature at which the fuel is stored or used. In one embodiment,
the concentration is at a level of up to about 20% by weight of the
emulsified fuel, and in one embodiment about 0.1% to about 20% by
weight, and in one embodiment about 1% to about 10% by weight of
the emulsified fuel.
[0128] Engines
[0129] The engines that may be operated in accordance with the
invention include all (internal combustion) engines including spark
ignited (gasoline) and compression ignited (diesel) for both mobile
including locomotive, marine, automotive, truck, heavy duty,
aviation and the like, and stationary power plants. The engines may
be two-cycle or four-cycle. The engines may employ conventional
after treatment devices. Included are on- and off-highway engines,
including new engines as well as in-use engines.
[0130] An open-flame burning apparatus may be operated with the
emulsified water fuel blend of the invention. The open-flame
burning apparatus may be any open-flame burning apparatus equipped
to burn a liquid fuel. These include domestic, commercial and
industrial burners. The industrial burners include those requiring
preheating for proper handling and atomization of the fuel. Also
included are oil fired combustion units, oil fired power plants,
fired heaters and boilers, and boilers for use in ships including
deep draft vessels. The fuel burning apparatus may be a boiler for
commercial applications included are boilers for power plants,
utility plants, and large stationary and marine engines. The
open-flame fuel burning apparatus may be an incinerator or a rotary
kiln incinerator, liquid injection kiln, fluidized bed kiln, cement
kiln, and the like. Also included are steel and aluminium forging
furnaces. The open-flame burning apparatus may be equipped with a
flue gas recirculation system.
[0131] From the above description and examples the invention those
skilled in the art may perceive improvements, changes and
modifications in the invention. Such improvement changes and
modifications are intended to be covered by the appended
claims.
* * * * *