U.S. patent application number 10/036145 was filed with the patent office on 2002-07-11 for emulsified water-blended fuel compositions.
This patent application is currently assigned to The Lubrizol Corporation. Invention is credited to Filippini, Brian B., Mullay, John J., Ray, James C., Steckel, Thomas F., Sweet, William R..
Application Number | 20020088167 10/036145 |
Document ID | / |
Family ID | 27496059 |
Filed Date | 2002-07-11 |
United States Patent
Application |
20020088167 |
Kind Code |
A1 |
Filippini, Brian B. ; et
al. |
July 11, 2002 |
Emulsified water-blended fuel compositions
Abstract
An emulsified water-blended fuel composition comprising: (A)
about 50% to about 99% by weight of a hydrocarbon fuel; (B) about
1% to about 50% by weight of water; (C) about 0.1% to about 10% of
a minor emulsifying amount of at least one fuel-soluble salt
comprised of (I) a first acylating agent, said first acylating
agent having at least one hydrocarbyl substituent of about 20 to
500 carbon atoms and a molecular weight (Mn) in the range of about
500 Mn to 10,000 Mn, (II) a second acylating agent, said second
acylating agent selected from the group consisting of
monocarboxylic agents, polycarboxylic agents, dicarboxylic agents
and combinations thereof; and wherein said second acylating agent
has at least 1 hydrocarbyl substituent of up to about 35 carbon
atoms and reacting said carboxylic acylating agents (I) and (II)
with (III) an ammonia or an amine to form a salt; (D) about 0.001%
to about 15% by weight of the water-soluble salt distinct from
component (C).
Inventors: |
Filippini, Brian B.;
(Mentor, OH) ; Sweet, William R.; (Richmond
Heights, OH) ; Steckel, Thomas F.; (Chagrin Falls,
OH) ; Mullay, John J.; (Mentor, OH) ; Ray,
James C.; (Mentor, OH) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION
Patent Dept. -Patent Adminstrator-022B
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Assignee: |
The Lubrizol Corporation
Wickliffe
OH
|
Family ID: |
27496059 |
Appl. No.: |
10/036145 |
Filed: |
October 22, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10036145 |
Oct 22, 2001 |
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09152852 |
Sep 14, 1998 |
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10036145 |
Oct 22, 2001 |
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09390925 |
Sep 7, 1999 |
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09390925 |
Sep 7, 1999 |
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09349268 |
Jul 7, 1999 |
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09349268 |
Jul 7, 1999 |
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09483481 |
Jan 14, 2000 |
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Current U.S.
Class: |
44/301 ; 44/302;
44/408 |
Current CPC
Class: |
C10L 1/328 20130101 |
Class at
Publication: |
44/301 ; 44/302;
44/408 |
International
Class: |
C10L 001/22 |
Claims
1. An emulsified water-blended fuel composition comprising: (A)
about 50% to about 99% by weight of a hydrocarbon fuel; (B) about
1% to about 50% by weight of water; (C) about 0.1% to about 10% of
a minor emulsifying amount of at least one fuel-soluble salt
comprised of (I) a first acylating agent, said first acylating
agent having at least one hydrocarbyl substituent of about 20 to
500 carbon atoms and a molecular weight (Mn) in the range of about
500 Mn to 10,000 Mn, (II) a second acylating agent, said second
acylating agent selected from the group consisting of
monocarboxylic agents, polycarboxylic agents, dicarboxylic agents
and combinations thereof; and wherein said second acylating agent
has at least 1 hydrocarbyl substituent of up to about 35 carbon
atoms and reacting said carboxylic acylating agents (I) and (II)
with (III) an ammonia or an amine to form a salt; (D) about 0.001%
to about 15% by weight of the water-soluble salt distinct from
component (C).
2. The composition of claim 1 wherein (C)(I) is a polycarboxylic
acid and (C)(II) is a monocarboxylic acid.
3. The composition of claim 1 wherein (C)(II) is a monocarboxylic
acid.
4. The composition of claim 1 wherein the first acylating agent is
a hydrocarbyl-substituted succinic acid represented by the formula
20wherein R is a hydrocarbyl group of about 30 to about 500 carbon
atoms.
5. The composition of claim 2 wherein the monocarboxylic acid is a
fatty acid and the polycarboxylic acid is a
polyisobutylene-substituted succinic acid.
6. The composition of claim 1 wherein the first acylating agent has
a molecular weight in the range of about 1000 Mn to about 5000
Mn.
7. The composition of claim 1 wherein the monocarboxylic agent
comprises oleic acid, isostearic acid, palmitic acid, stearic acid,
linoleic acid, arachidic acid, tall oil fatty acids, gadoleic acid,
behenic acid, erucic acid, ligoceric acid or combinations
thereof.
8. The composition of claim 1 wherein the first acylating agent
component (C)(I) is selected from the group comprising a
polyisobutene substitute succinic acid and the second acylating
agent, component (C)(II) is selected from the group consisting of
oleic acid, isostearic acid, palmitic acid, stearic acid, linoleic
acid, tall oil fatty acids, arachidic acid, gadoleic acid, behenic
acid, erucic acid, ligoceric acid and combinations thereof.
9. The composition of claim 1 wherein the ratio of (C)(I) to
(C)(II) in the water-blended fuel composition is in the range of
about 9 to about 1 to about 1 to about 9.
10. The composition of claim 1 wherein the ratio of (C)(I) to
(C)(II) in the water-blended fuel composition is in the range of
about 1 to about 3 to about 3 to about 1.
11. The composition of claim 1 wherein the product of the reaction
between acylating agents (C)(I) and (C)(II) with the ammonia or the
amine are carboxylate salts and combinations thereof.
12. The composition of claim 11 wherein the acylating agents (C)(I)
and (C)(II) are carboxylic acids.
13. The composition of claim 1 wherein (C)(III) is selected from
the group comprising monoamines, polyamines, hydroxyamines and
combinations thereof.
14. The composition of claim 1 wherein (D) is represented by the
formula K[G(NR.sub.3).sub.y].sup.y+nX.sup.p-and wherein g is
hydrogen, or an organic neutral radical of 1 to about 8 carbon
atoms having a valence of y; each R independently is hydrogen or a
hydrocarbyl group of 1 to about 10 carbon atoms; X.sup.p-is an
anion having a valence of p; and k, y, n and p are independently at
least 1, provided that when G is H, y is 1; and further provided
that the sum of the positive charge ky.sup.+ is equal to the sum of
the negative charge np.sup.- such that the amine salt is
electrically neutral.
15. The composition of claim 1 wherein component (D) comprises
ammonium nitrate, ammonium acetate, methylammonium nitrate, methyl
ammonium acetate, ethylene diamine diacetate, urea nitrate,
guanidium nitrate or combinations thereof.
16. The composition of claim 1 wherein component (D) is ammonium
nitrate.
17. The composition of claim 1 further comprises at least one
organic cetane improver.
18. The composition of claim 1 further comprises at least one
antifreeze.
19. The composition of claim 1 further comprises at least one
alcohol selected from the group consisting of methanol, ethanol,
ethylene glycol, propylene glycol, glycerol and combinations
thereof.
20. The composition of claim 1 further comprises an additional
emulsifier comprising an ionic or nonionic compound having a
hydrophilic lipophilic balance in the range of about 1 to about
40.
21. The composition of claim 1 wherein the hydrocarbon fuel is
selected from the group consisting of gasoline; diesel; gasoline
and ethanol; diesel fuel and ether; gasoline and a biodegradable
resource; diesel fuel and a biodegradable resource; biodegradable
fuels; renewable resources; and combinations thereof.
22. The composition of claim 21 wherein the hydrocarbon fuel is
selected from the group consisting of a biodegradable resource, a
biodegradable fuel, a renewable resource and combinations thereof
in the range from about 0.1% to about 10% of the hydrocarbon
fuel.
23. The composition of claim 21 wherein the hydrocarbon fuel is
selected from the group consisting of a biodegradable resource, a
biodegradable fuel, a renewable resource and combinations thereof
in the range from about 2% to about 20% of the hydrocarbon
fuel.
24. The composition of claim 1 wherein the hydrocarbon fuel is
selected from the group consisting of a biodegradable resource, a
biodegradable fuel, a renewable resource and combinations thereof
in the range from about 20% to about 100% of the hydrocarbon
fuel.
25. A process for fueling an internal combustion engine comprising
fueling the engine with the fuel composition of claim 1.
Description
[0001] This application is a continuation in part of U.S.
Application Ser. No. 09/152,852, filed Sep. 14, 1998, and also a
continuation in part of U.S. application Ser. No. 09/390,925, filed
on Sep. 7, 1999, that is a continuation in part of U.S. application
Ser. No. 09/349,268, filed Jul. 7, 1999, that is a continuation in
part of 09/483,481. Each of the disclosures of the prior
applications is in incorporated herein by reference, in their
entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to emulsified water-blended
fuel compositions, more particularly to water-blended fuel
compositions containing a liquid fuel, water, an emulsifier, and an
amine salt which may function as an emulsion stabilizer or
combustion modifier. In one embodiment of the invention, the
composition further comprises an organic cetane improver, and in
one embodiment an antifreeze.
DESCRIPTION OF THE RELATED ART
[0003] Internal combustion engines, especially diesel engines using
a mixture of water and fuel in the combustion chamber can produce
lower NOx, hydrocarbon and particulate emissions per unit of power
output. Water is inert toward combustion, but acts to lower peak
combustion temperatures that result in less NOx formation. Exhaust
Gas Recirculation (EGR) works on the same principle; that is, inert
materials tend to lower peak combustion temperatures and hence
reduce NOx. Water can be separately injected into the cylinder, but
hardware costs are high. Water can also be added to the fuel as an
emulsion. However, emulsion stability has historically been a
problem.
[0004] It would be advantageous to provide a water-blended fuel
composition that has improved emulsion stability. The present
invention provides such an advantage.
[0005] U.S. Pat. No. 5,669,938, Schwab, Sep. 23, 1997, discloses a
fuel composition which consists of (i) a water-in-oil emulsion
comprising a major proportion of a hydrocarbonaceous middle
distillate fuel and about 1 to 40 volume percent water, (ii) a CO
emission, and particulate matter emission reducing amount of at
least one fuel-soluble organic nitrate ignition improver, and
optionally containing (iii) at least one component selected from
the group consisting of di-hydrocarbyl peroxides, surfactants,
dispersants, organic peroxy esters, corrosion inhibitors,
antioxidants, antirust agents, detergents, lubricity agents,
demulsifiers, dyes, inert diluents, and a cyclopentadienyl
manganese tricarbonyl compound.
[0006] European Patent EP 0 475 620 B 1, Sexton et al., August 11,
1995, disclose a diesel fuel composition which comprises: (a) a
diesel fuel; (b) 1.0 to 30.0 weight percent of water based upon
said diesel fuel; (c) a cetane number improver additive, present in
an amount up to, but less than, 20.0 weight percent based upon said
water, said additive being selected from an inorganic oxidizer, a
polar organic oxidizer and a nitrogen oxide-containing
compound;
[0007] and (d) 0.5 to 15.0 wt. % based on the diesel fuel of a
surfactant system comprising (i) one or more first surfactants
selected from surfactants capable of forming a lower phase
microemulsion at 20.degree. C. when combined with equal volumes of
the fuel and water at a concentration of 2 grams of surfactant per
deciliter of fuel plus water, which microemulsion phase has a
volume ratio of water to surfactant of at least 2; at least one
said first surfactant being an ethoxylated C.sub.12-C.sub.18 alkyl
ammonium salt of a C.sub.9-C.sub.24 alkyl carboxylic or alkylaryl
sulfonic acid containing 6 or more ethylene oxide groups; and (ii)
one or more second surfactants selected from surfactants capable of
forming an upper phase microemulsion at 20.degree. C. when combined
with equal volumes of the fuel and water at a concentration of 2
grams of surfactant per deciliter of fuel plus water, which
microemulsion phase has a volume ratio of water to surfactant of at
least 2; at least one said surfactant being an ethoxylated
C.sub.12-C.sub.18 alkyl ammonium salt of C.sub.9-C.sub.24 alkyl
carboxylic or alkylaryl sulfonic acid containing less than 6
ethylene oxide groups; the said first and second surfactants being
present in a weight ratio which forms with components (a), (b) and
(c) a single phase translucent microemulsion.
[0008] European patent publication EP 0 561 600 A2, Jahnke, Sep.
22, 1993, discloses a water in oil emulsion comprising a
discontinuous aqueous phrase comprising at least one
oxygen-supplying component (such as ammonium nitrate); a continuous
organic phase comprising at least one carbonaceous fuel; and a
minor emulsifying amount of at least one emulsifier made by the
reaction of:
[0009] (A) at least one substituted succinic acylating agent, said
substituted acylating agent consisting of substituent groups and
succinic groups wherein the substituent groups are derived from a
polyalkene, said acylating agents being characterized by the
presence within their structure of an average of at least 1.3
succinic groups for each equivalent weight of substituent groups,
and (B) ammonia and/or at least one amine.
[0010] U.S. Pat. No. 5,047,175, Forsberg, Sep. 10, 1991, discloses
salt compositions which comprise: (A) at least one salt moiety
derived from (A)(I) at least one high-molecular weight
polycarboxylic acylating agent, said acylating agent (A)(I) having
at least one hydrocarbyl substituent having an average of from
about 20 to about 500 carbon atoms, and (A)(II) ammonia, at least
one amine, at least one alkali or alkaline earth metal, and/or at
least one alkali or alkaline earth metal compound; (B) at least one
salt moiety derived from (B)(I) at least one low-molecular weight
polycarboxylic acylating agent, said acylating agent (B)(I)
optionally having at least one hydrocarbyl substituent having an
average of up to about 18 carbon atoms, and (B)(II) ammonia, at
least one amine, at least one alkali or alkaline earth metal,
and/or at least one alkali or alkaline earth metal compound; said
components (A) and (B) being coupled together by (C) at least one
compound having (i) two or more primary amino groups, (ii) two or
more secondary amino groups, (iii) at least one primary amino group
and at least one secondary amino group, (iv) at least two hydroxyl
groups or (v) at least one primary or secondary amino group and at
least one hydroxyl group. These salt compositions are disclosed to
be useful as emulsifiers in water-in-oil explosive emulsions,
particularly cap-sensitive water-in-oil emulsions.
[0011] U.S. Pat. No. 4, 708,753, Forsberg, Nov. 24, 1987, discloses
a water-in-oil emulsion comprising (A) a continuous oil phase; (B)
a discontinuous aqueous phase; (C) a minor emulsifying amount of at
least one salt derived from (C)(1) at least one
hydrocarbyl-substituted carboxylic acid or anhydride, or ester or
amide derivative of said acid or anhydride, the hydrocarbyl
substituent of (C)(I) having an average of from about 20 to about
500 carbon atoms, and (C)(II) at least one amine; and (D) a
functional amount of at least one water-soluble, oil-insoluble
functional additive dissolved in said aqueous phase; with the
proviso that when component (D) is ammonium nitrate, component (C)
is other than an ester/salt formed by the reaction of
polyisobutenyl (M.sub.n=950) succinic anhydride with diethanolamine
in a ratio of one equivalent of anhydride to one equivalent of
amine.
[0012] U.S. Pat. No. 3,756,794, Ford, Sep. 4, 1973, discloses an
emulsified fuel composition consisting essentially of (1) a major
amount of a hydrocarbon fuel boiling in the range of 20-400.degree.
C. as the disperse phase, (2) 0.3% to 5% by weight of an
emulsifier, (3) 0.75% to 12% by weight water, (4) 0.3% to 0.7% by
weight of urea as emulsion stabilizer and (5) 0.3% to 0.7% by
weight of ammonium nitrate.
SUMMARY OF THE INVENTION
[0013] This invention relates to an emulsified water-blended fuel
composition comprising:
[0014] (A) about 50% to about 99% by weight of a hydrocarbon
fuel;
[0015] (B) about 1% to about 50% by weight of water;
[0016] (C) about 0.1% to about 10% of a minor emulsifying amount of
at least one fuel-soluble salt comprised of (I) a first acylating
agent, said first acylating agent having at least 1.0 one
hydrocarbyl substituent of about 20 to 500 carbon atoms and a
molecular weight (Mn) in the range of about 500 Mn to 10,000 Mn,
(II) a second acylating agent, said second acylating agent selected
from the group consisting of monocarboxylic agents, polycarboxylic
agents, dicarboxylic agents and combinations thereof; and wherein
said second acylating agent has at least 1 hydrocarbyl substituent
of up to about 35 carbon atoms and reacting said carboxylic
acylating agents (I) and (II) with (III) an ammonia or an amine to
form a salt; and
[0017] (D) about 0.001% to about 15% by weight of the water-soluble
salt distinct from component (C).
[0018] In one embodiment, the composition further comprises at
least one organic cetane improver; and in one embodiment, at least
one antifreeze, and in one embodiment at least one alcohol.
[0019] In the preferred embodiment, this invention relates to an
emulsified water-blended fuel composition comprising: (A) a
hydrocarbon fuel; (B) water; (C) a minor emulsifying amount of at
least one fuel-soluble salt comprised of (I) a first acylating
acid, said first acylating acid having at least one hydrocarbyl
substituent of about 20 to about 500 carbon atoms and a molecular
weight (Mn) of about 500 to 10,000 (II) a second acylating agent
having at least one hydrocarbyl substituent of up to about 35
carbon atoms, and reacting said acylating agents (I) and (II)
forming a salt with (III) ammonia or an amine; and (D) about 0.001%
to about 15% by weight of a water-soluble salt distinct from
component (C). In the preferred embodiment the first acylating
agent is a polycarboxylic acid and the second acylating agent is a
monocarboxylic acid.
[0020] The water-blended fuel composition is comprised of droplets
having a mean diameter of 1.0 micron or less. In one embodiment the
mean droplet size is less than about 0.95 micron, in one embodiment
less than about 0.8 micron, and in one embodiment less than about
0.7 micron. In one embodiment the mean droplet size is in the range
of about 0.1 to about 0.95, in one embodiment about 0.1 to about
0.7 micron, in one embodiment 0.1 to about 0.5 micron. In one
embodiment, the droplet size is in the range of about 1.0 to about
0.5 micron.
DETAILED DESCRIPTION OF THE INVENTION
[0021] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is well
known to those skilled in the art. Specifically, it refers to a
group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
[0022] (1) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form an alicyclic radical);
[0023] (2) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy);
[0024] (3) hetero substituents, that is, substituents which, while
having a predominantly hydrocarbon character, in the context of
this invention, contain other than carbon in a ring or chain
otherwise composed of carbon atoms. Heteroatoms include sulfur,
oxygen, nitrogen, and encompass substituents as pyridyl, furyl,
thienyl and imidazolyl. In general, no more than two, preferably no
more than one, non-hydrocarbon substituent will be present for
every 10 carbon atoms in the hydrocarbyl group; typically, there
will be no non-hydrocarbon substituents in the hydrocarbyl
group.
[0025] The term "hydrocarbylene group" refers to a divalent analog
of a hydrocarbyl group.
[0026] Examples of hydrocarbylene groups include ethylene
(--CH.sub.2CH.sub.2--), propylene (both linear and branched), and
2-octyloxy-1,3-propylene
(--CH.sub.2CH(OC.sub.8H.sub.17)CH.sub.2--).
[0027] The phrase "reactive equivalent" of a material means any
compound or chemical composition other than the material itself
that reacts or behaves like the material itself under the reaction
conditions. Thus for example, reactive equivalents of carboxylic
acids include acid-producing derivatives such as anhydrides, acyl
halides, and mixtures thereof unless specifically stated
otherwise.
[0028] The term "lower" when used in conjunction with terms such as
alkyl, alkenyl, and alkoxy, is intended to describe such groups
that contain a total of up to 7 carbon atoms.
[0029] The term "water-soluble" refers to materials that are
soluble in water to the extent of at least one gram per 100
milliliters of water at 25.degree. C.
[0030] The term "fuel-soluble" refers to materials that are soluble
in fuel (gasoline or diesel) to the extent of at least one gram per
100 milliters of fuel at 25.degree. C. It also refers to materials
that end up mostly in the fuel phase when a mixture of a certain
quantity of the material and equal volume of fuel and water are
mixed together, leaving the water phase substantially (greater than
90%) free of the material.
[0031] In one embodiment of the present composition, the components
are mixed together to form a water-in-fuel emulsion with the
hydrocarbon fuel being the continuous phase, and water being the
discontinuous phase dispersed in the hydrocarbon fuel phase.
[0032] The components of the emulsified water-blended fuel
composition are described in detail hereunder.
[0033] The Hydrocarbon Fuel (A)
[0034] The liquid hydrocarbon fuel comprises hydrocarbonaceous
petroleum distillate fuel, non-hydrocarbonaceous materials that
include but are not limited to oils, liquid fuels derived from
vegetables, rapeseed, ethanol, liquid fuels derived from minerals
and mixtures thereof and combinations thereof. Liquid hydrocarbon
fuel may be any and all hydrocarbonaceous petroleum distillate
fuels including but not limited to gasoline, diesel fuel, fuel oil,
biodegradable fuels, biodiesel fuels and the like. The liquid
hydrocarbon fuels comprising non-hydrocarbonaceous materials
include but are not limited to alcohols, such as methanol, ethanols
and the like; ether such as diethyl ether, methyl ethyl ether and
the like; liquid fuels derived from vegetable sources such as corn,
alfalfa, rapeseed, and mineral sources such as shale, coal and the
like. Liquid hydrocarbon fuels also include mixtures of one or more
hydrocarbonaceous and one or more non-hydrocarbonaceous materials.
Examples of such mixtures are combinations of gasoline and ethanol,
a diesel fuel and ether, gasoline and a biodegradable fuel, diesel
fuel and a biodegradable fuel, and gasoline or diesel fuel with a
renewable resource additive or fuel.
[0035] The hydrocarbon fuel contains in one embodiment
biodegradable fuel, biodegradable fuel additive, renewable
resource, additive renewable resource or mixtures thereof in the
range of about 0.1% to about 100%, in another embodiment about 2%
to about 75%, in another embodiment about 10% to about 50%, in
another embodiment about 2% to about 15%, in another embodiment
about 100%.
[0036] In one embodiment one component of the composition of this
invention is a hydrocarbon fuel boiling in the gasoline or diesel
range. Motor gasoline is defined by ASTM Specifications D-439-89.
It comprises a mixture of hydrocarbons having an ASTM boiling point
of 60.degree. C. at the 10% distillation point to about 205.degree.
C. at the 90% distillation point. The fuel may contain alcohols,
esters, biodegradable materials and combinations thereof. In one
embodiment, the fuel is a chlorine-free or low-chlorine gasoline
characterized by a chlorine content of no more than about 10 ppm.
In one embodiment the gasoline fuel has a sulfur content of about
up to about 0.05% by weight as determined by the test method
specified in ASTM D 2622-87.
[0037] In one embodiment the diesel fuels that are useful with this
invention can be any diesel fuel. They include those that are
defined by ASTM Specification D396. In one embodiment the diesel
fuel has a sulfur content of up to about 0.05% by weight
(low-sulfur diesel fuel) as determined by the test method specified
in ASTM D 2622-87 entitled "Standard Test Method for Sulfur in
Petroleum Products by X-Ray Spectrometry." Any fuel having a
boiling range and viscosity suitable for use in a diesel-type
engine can be used.
[0038] These fuels typically have a 90% point distillation
temperature in the range of about 300.degree. C. to about
390.degree. C., and in one embodiment about 330.degree. C. to about
350.degree. C. The viscosity for these fuels typically ranges from
about 1.3 to about 24 centistokes at 40.degree. C. These diesel
fuels can be classified as any of Grade Nos. 1-D, 2-D or 4-D as
specified in ASTM D 975 entitled "Standard Specification for Diesel
Fuel Oils." These diesel fuels may contain alcohols, esters,
biodegradable materials and mixtures thereof. In one embodiment,
the diesel fuel is a chlorine-free or low-chlorine diesel fuel
characterized by a chlorine content of no more than about 10 ppm.
In one embodiment the diesel fuel has a sulfur content of about up
to about 0.05% by weight as determined by the test method specified
in ASTM D 2622-87.
[0039] The liquid hydrocarbon fuel present in the emulsified
water-blended fuel is at a concentration in the range of about 50%
to about 95% by weight, in one embodiment about 60% to about 95% by
weight, in one embodiment about 65% to about 85% by weight, and in
one embodiment about 80% to about 90% by weight of the emulsified
water-blended fuel.
[0040] The Acylating Agent (C)(I)
[0041] The acylating agent (C)(I) is a hydrocarbyl-substituted
succinic acid or anhydride (A) or a carboxylic acid, and may be
represented by the formulae 1
[0042] wherein in each of the above formulae, R is a hydrocarbyl
group of about 30 to about 500arbon at the material has a Mn of 500
to 10,000, and in one embodiment from 500 to 500 carbon atoms and
the material has a Mn of about 500 to about 10,000, and in one
embodiment about 1000, and in one embodiment from about 1000 to
about 5000, and in one embodiment from about 1000 to about
3000.
[0043] In a one embodiment, the acylating agent (C)(I) is a
hydrocarbyl-substituted succinic acid and may be derived from the
reaction of water with the corresponding succinic anhydride 2
[0044] The carboxylic acids may also be derived from other
acylating agent such a carboxylic acid anhydrides, acids, esters,
amides, nitrites via reactions well known to those skilled in the
art.
[0045] In one embodiment, the carboxylic acid or the acylating
agent (C)(I) used to prepare the carboxylic acid is made by
reacting one or more alpha-beta olefinically unsaturated carboxylic
acid reagents containing 2 to about 20 carbon atoms, exclusive of
the carboxyl based groups, with one or more olefin polymers
containing at least about 20 carbon atoms, as described more fully
hereinafter.
[0046] The alpha-beta olefinically unsaturated carboxylic acids may
be either monobasic or polybasic in nature. Exemplary of the
monobasic alpha-beta olefinically unsaturated carboxylic acids
include the carboxylic acids corresponding to the formula 3
[0047] wherein in formula (C-I-2), R is hydrogen, or a saturated
aliphatic or alicyclic, aryl, alkylaryl or heterocyclic group,
preferably hydrogen or a lower alkyl group, and R.sup.1 is hydrogen
or a lower alkyl group. The total number of carbon atoms in R and
R.sup.1 should not exceed about 18 carbon atoms. Specific examples
of useful monobasic alpha-beta olefinically unsaturated carboxylic
acids include acrylic acid; methacrylic acid; cinnamic acid;
crotonic acid; 3-phenyl propenoic acid; alpha, and beta-decenoic
acid. The polybasic acids are preferably dicarboxylic, although
tri- and tetracarboxylic acids can be used. Exemplary polybasic
acids include maleic acid, fumaric acid, mesaconic acid, itaconic
acid and citraconic acid.
[0048] Reactive equivalents of the alpha-beta olefinically
unsaturated carboxylic acid reagents include the anhydride, ester
or amide functional derivatives of the foregoing acids.
[0049] A preferred alpha-beta olefinically unsaturated carboxylic
acid is maleic anhydride.
[0050] In the preferred embodiment, the acylating agent (C)(I) of
this invention is a hydrocarbyl-substituted succinic acid
represented correspondingly by the formulae 4
[0051] wherein in formula (C-I-3), R is hydrocarbyl group of about
30 to about 500 carbon atoms and the material has a Mn of 500 to
10,000, and in one embodiment from 1000 to 5000. 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 well known to those
of skill in the art and need not be discussed in detail herein.
[0052] The hydrocarbyl group "R" of the substituted succinic acids
and anhydrides of formula (C-I-3) can thus be derived from olefin
polymers or chlorinated analogs thereof. The olefin monomers from
which the olefin polymers are derived are polymerizable olefin
monomers characterized by having one or more ethylenic unsaturated
groups. They can be monoolefinic monomers such as ethylene,
propylene, butene-1, isobutene and octene-1 or polyolefinic
monomers (usually di-olefinic monomers such as butadiene-1,3 and
isoprene). Usually these monomers are terminal olefins, that is,
olefins characterized by the presence of the group>C=CH.sub.2.
However, certain internal olefins can also serve as monomers (these
are sometimes referred to as medial olefins). When such medial
olefin monomers are used, they normally are employed in combination
with terminal olefins to produce olefin polymers that are
interpolymers. Although, the hydrocarbyl substituents may also
include aromatic groups (especially phenyl groups and lower alkyl
and/or lower alkoxy-substituted phenyl groups such as
para(tertiary-butyl)-phenyl groups) and alicyclic groups such as
would be obtained from polymerizable cyclic olefins or
alicyclic-substituted polymerizable cyclic olefins, the
hydrocarbyl-based substituents are usually free from such groups.
Nevertheless, olefin polymers derived from such interpolymers of
both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or
para-(tertiary butyl) styrene are exceptions to this general
rule.
[0053] Generally the olefin polymers are homo- or interpolymers of
terminal hydrocarbyl olefins of about 2 to about 30 carbon atoms,
and in one embodiment about 2 to about 16 carbon atoms. A more
typical class of olefin polymers is selected from that group
consisting of homo- and interpolymers of terminal olefins of 2 to
about 6 carbon atoms, and in one embodiment 2 to about 4 carbon
atoms.
[0054] Specific examples of terminal and medial olefin monomers
that can be used to prepare the olefin polymers from which the
hydrocarbyl-based substituents are derived include ethylene,
propylene, butene-1, butene-2, isobutene, pentene-1, hexene-1,
heptene-1, octene-1, nonene-1, decene-1, pentene-2, propylene
tetramer, diisobutylene, isobutylene trimer, butadiene-1,2,
butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isoprene,
hexadiene-1,5, 2-chlorobutadiene-1,3, 2-methylheptene-1,
3-cyclohexylbutene-1, 3 ,3-dimethylpentene-1,
styrenedivinylbenzene, vinyl-acetate allyl
alcohol,1-methylvinylacetate, acrylonitrile, ethyl acrylate,
ethylvinylether and methyl-vinylketone. Of these, the purely
hydrocarbyl monomers are more typical and the terminal olefin
monomers are especially typical.
[0055] In one embodiment, the olefin polymers are polyisobutylenes
such as those obtained by polymerization of a C.sub.4 refinery
stream having a butene content of about 35 to about 75% by weight
and an isobutene content of about 30 to about 60% by weight in the
presence of a Lewis acid catalyst such as aluminum chloride or
boron trifluoride. These polyisobutylenes generally contain
predominantly (that is, greater than about 50 percent of the total
repeat units) isobutene repeat units of the configuration 5
[0056] In one embodiment, the hydrocarbyl group R is a
polyisobutene group having an average of about 30 to about 500
carbon atoms and a Mn of about 500 to 10,000, and in one embodiment
from about 1000 to 5000, and in one embodiment from about 1000 to
3000.
[0057] Gel permeation chromatography (GPC) (also known as size
exclusion chromatography (SEC)) is a method that can provide both
weight average and number average molecular weights as well as the
entire molecular weight distribution of polymers.
[0058] For purposes of this invention, a series of fractionate
polymers of isobutene (isobutylene) is used as the calibration
standard in the GPC. The techniques for determining number average
molecular weight (Mn) and weight average molecular weight 9mw) of
polymers are well known and are described in numerous books and
articles, For example, methods for the determination of Mn and
molecular weight distribution of polymers is described in W.W. Yan,
J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography," J. Wiley & Sons, Inc., 1979.
[0059] In addition to being described in terms of carbon numbers,
the polyolefin substituents of the hydrocarbyl-substituted succinic
acids and anhydrides of this invention can also be described in
terms of their number average and/or weight average molecular
weights. An approximate method to convert the number average
molecular weight of the polyolefin to number of carbon atoms is to
divide the number average molecular weight by 14.
[0060] The olefin polymer can be any olefin polymer that has been
described hereinbefore in relation to substituent "R" in formula
(C-I-3) above. The "succinic groups" are those groups characterized
by the structure 6
[0061] wherein in structure (C-I-4), X and X' are the same or
different provided that at least one of X and X' is such that the
substituted succinic acylating agent can function as a carboxyl
acylating agent.
[0062] Thus, X and/or X' is usually --OH, --O--hydrocarbyl,
--)--M.sup.+ where M.sup.+ represents one equivalent of a metal,
ammonium or amine cation, --NH.sub.2, --Cl, --Br, and together, X
and X' can be --O-- so as to form the anhydride. The specific
identity of any X or X' group which is not one of the above is not
critical so long as its presence does not prevent the remaining
group from entering into acylation reactions. Preferably, however,
X and X' are each such that both carboxyl functions of the succinic
group (i.e., both --C(O)X and --C(O)X') can enter into acylation
reactions.
[0063] One of the unsatisfied valences in the grouping 7
[0064] of formula (C-I-4) forms a carbon-carbon bond with a carbon
atom in the hydrocarbyl substituent group. While other such
unsatisfied valence may be satisfied by a similar bond with the
same or different substituent group, all but the said one such
valence is usually satisfied by hydrogen; i.e., --H.
[0065] In one embodiment, the succinic groups correspond the
formula 8
[0066] wherein in formula (C-I-5), R and R' are each independently
selected from the group consisting of --OH, --Cl, --O--lower alkyl,
and when taken together, R and R' equal --O--. In the latter case,
the succinic group is a succinic anhydride group. All the succinic
groups in a particular succinic acylating agent need not be the
same, but they can be the same. In one embodiment, the succinic
groups correspond to 9
[0067] or mixtures of (C-I-6)(a) and (C-I-6)(b). Providing
hydrocarbyl-substituted succinic acylating agents wherein the
succinic groups are the same or different is within the ordinary
skill of the art and can be accomplished through conventional
procedures such as treating the hydrocarbyl substituted succinic
acylating agents themselves (for example, hydrolyzing the anhydride
to the free acid) and/or selecting the appropriate maleic or
fumaric reactants.
[0068] Partial esters of the succinic acids or anhydrides can be
prepared simply by the reaction of the acid or anhydride with an
alcohol or phenolic compound. Particularly useful are the lower
alkyl and alkenyl alcohols such as methanol, ethanol, allyl
alcohol, propanol, cyclohexanol, etc. Esterification reactions are
usually promoted by the use of alkaline catalysts such as sodium
hydroxide or alkoxide, or an acidic catalyst such as sulfuric acid
or toluene sulfonic acid. A partial ester can be represented by the
formula 10
[0069] wherein in formula (C-I-7), R is a hydrocarbyl group; and R'
is a hydrocarbyl group, typically a lower alkyl group. In one
embodiment, component (C) of the present invention includes the
salt compositions of U.S. Pat. No. 5,047,175 ("the '175 patent),
except for those salt compositions of the '175 patent which are
derived from reacting alkali metal, alkaline earth metal, alkali
metal compound, or alkaline earth metal compounds (which fall
within components (A)(II) and (B)(II) of the '175 patent). Thus in
one embodiment of the present invention, component (C)(I) is made
by coupling a) at least one polyisobutene substituted succinic acid
or anhydride, the polyisobutene substituent of said succinic acid
or anhydride having about 50 to about 200 carbon atoms, and in one
embodiment about 50 to about 150, and in one embodiment about 70 to
about 100 carbon atoms; and b) at least one hydrocarbyl-substituted
succinic acid or anhydride, the hydrocarbyl substituent of said
succinic acid or anhydride having up about 8 to about 25 carbon
atoms, and in one embodiment from about 10 to about 20 carbon
atoms, and in one embodiment about 16 carbon atoms; by (c) at least
one coupling agent having (i) two or more primary amino groups,
(ii) two or more secondary amino groups, (iii) at least one primary
amino group and at least one secondary amino group, (iv) at least
two hydroxyl groups or (v) at least one primary or secondary amino
group and at least one hydroxyl group.
[0070] The coupling agent includes those components described under
component (C) of the '175 patent, including polyamines, polyols,
and hydroxyamines. In one embodiment, the coupling agent of the
present invention is ethylene glycol.
[0071] In one embodiment the acylating agent (C)(I) comprises at
least one compound represented by the formula 11
[0072] wherein R.sup.1 is a polyisobutene group of about 35 to
about 300 carbon atoms and R.sup.2 is a hydrocarbyl group of about
10 to 20 carbon atoms. This compound can be seen as the result of
coupling a R.sup.1 substituted succinic acid or anhydride with an
R.sup.2 substituted succinic acid or anhydride by the coupling
agent ethylene glycol.
[0073] In addition to the methods described in the '753 patent and
in EP 0 561 600 A2 for the preparation of the acylating agents of
this invention, such as the one step, two step and direct
alkylation procedures, the acylating agents of the present
invention can also be made via a direct alkylation procedure that
does not use chlorine. Polyisobutene-substitute- d succinic
anhydride produced by such a process is available from Texaco under
the name TLA.TM.-629C.
[0074] The Carboxylic Acid (C)(II)
[0075] The acylating agent (C)(II) of this invention includes
carboxylic acids and their reactive equivalents such as acid
halides and anhydrides.
[0076] 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 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 and lignoceric acid. These
acids may be saturated, unsaturated, or have other functional
groups, such as hydroxyl groups, as in 12-hydroxy stearic acid,
from the hydrocarbyl backbone.
[0077] These carboxylic acids can also be obtained from
triglycerides represented by the formula 12
[0078] wherein in formula (C-I-1), R.sup.1, R.sup.2 and R.sup.3 are
independently hydrocarbyl groups such that the total number of
carbon atoms in the triglycerides ranges from about 12 to about
500. These triglycerides can be converted into monocarboxylic acid
by methods well known to those skilled in the art. The carboxylic
acids may be derived from other acylating agent such as carboxylic
acid anhydrides, acids, esters, amides, and nitriles via reactions
well known to those skilled in the art.
[0079] In one embodiment, the carboxylic acid (C)(II) of this
invention is a hydrocarbyl-substituted succinic acid represented
correspondingly by the formula 13
[0080] wherein in formula (C-I-3), R is hydrocarbyl group of about
12 to about 35 carbon atoms, 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. 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 well known to those
of skill in the art and need not be discussed in detail herein.
[0081] In one embodiment, the carboxylic acid (C)(II) or the
acylating agent used to prepare carboxylic acid (C)(II) is made by
reacting one or more alpha-beta olefinically unsaturated carboxylic
acid reagents containing 2 to about 20 carbon atoms, exclusive of
the carboxyl based groups, with one or more olefin polymers
containing at least about 16carbon atoms, as described more fully
hereinafter.
[0082] The alpha-beta olefinically unsaturated carboxylic acids may
be either monobasic or polybasic in nature. Exemplary of the
monobasic alpha-beta olefinically unsaturated carboxylic acids
include the carboxylic acids corresponding to the formula 14
[0083] wherein in formula (C-I-2), R is hydrogen, or a saturated
aliphatic or alicyclic, aryl, alkylaryl or heterocyclic group,
preferably hydrogen or a lower alkyl group, and R.sup.1 is hydrogen
or a lower alkyl group. The total number of carbon atoms in R and
R' should not exceed about 18 carbon atoms. Specific examples of
useful monobasic alpha-beta olefinically unsaturated carboxylic
acids include acrylic acid; methacrylic acid; cinnamic acid;
crotonic acid; 3-phenyl propenoic acid; alpha, and beta-decenoic
acid. The polybasic acids are preferably dicarboxylic, although
tri- and tetracarboxylic acids can be used. Exemplary polybasic
acids include maleic acid, fumaric acid, mesaconic acid, itaconic
acid and citraconic acid.
[0084] Reactive equivalents of the alpha-beta olefinically
unsaturated carboxylic acid reagents include the anhydride, ester
or amide functional derivatives of the foregoing acids. A preferred
alpha-beta olefinically unsaturated carboxylic acid is maleic
anhydride.
[0085] The hydrocarbyl group R of the substituted succinic acids
and anhydrides of formula (C-I-3) can thus be derived from olefin
polymers or chlorinated analogs thereof. The olefin monomers from
which the olefin polymers are derived are polymerizable olefin
monomers characterized by having one or more ethylenic unsaturated
groups. They can be monoolefinic monomers such as ethylene,
propylene, butene-1, isobutene and octene-1 or polyolefinic
monomers (usually di-olefinic monomers such as butadiene-1,3 and
isoprene). Usually these monomers are terminal olefins, that is,
olefins characterized by the presence of the group>C=CH.sub.2.
However, certain internal olefins can also serve as monomers (these
are sometimes referred to as medial olefins). When such medial
olefin monomers are used, they normally are employed in combination
with terminal olefins to produce olefin polymers that are
interpolymers. Although, the hydrocarbyl substituents may also
include aromatic groups (especially phenyl groups and lower alkyl
and/or lower alkoxy-substituted phenyl groups such as
para(tertiary-butyl)-phenyl groups) and alicyclic groups such as
would be obtained from polymerizable cyclic olefins or
alicyclic-substituted polymerizable cyclic olefins, the
hydrocarbyl-based substituents are usually free from such groups.
Nevertheless, olefin polymers derived from such interpolymers of
both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or
para-(tertiary butyl) styrene are exceptions to this general
rule.
[0086] Generally the olefin polymers are homo- or interpolymers of
terminal hydrocarbyl olefins of about 2 to about 30 carbon atoms,
and in one embodiment about 2 to about 16 carbon atoms. A more
typical class of olefin polymers is selected from that group
consisting of homo- and interpolymers of terminal olefins of 2 to
about 6 carbon atoms, and in one embodiment 2 to about 4 carbon
atoms.
[0087] Specific examples of terminal and medial olefin monomers
that can be used to prepare the olefin polymers from which the
hydrocarbyl-based substituents are derived include ethylene,
propylene, butene-1, butene-2, isobutene, pentene-1, hexene-1,
heptene-1, octene-1, nonene-1, decene-1, pentene-2, propylene
tetramer, diisobutylene, isobutylene trimer, butadiene-1,2,
butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isoprene,
hexadiene-1,5, 2-chlorobutadiene-1,3, 2-methylheptene-1,
3-cyclohexylbutene-1, 3,3-dimethylpentene-1, styrenedivinylbenzene,
vinyl-acetate allyl alcohol,1-methylvinylacetate, acrylonitrile,
ethyl acrylate, ethylvinylether and methyl-vinylketone. Of these,
the purely hydrocarbyl monomers are more typical and the terminal
olefin monomers are especially typical.
[0088] In the preferred embodiment, the ratio of the first
acylating agent (C)(I), to the second acylating agent (C)(II) in
the water-blended 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.
[0089] Component (C)(III)
[0090] Component (C)(III) of the present invention includes ammonia
and/or at least one amine. The amines useful for reacting with the
acylating agent (C)(I) of this invention include monoamines,
polyamines, or mixtures of these. These amines are described in
detail in the '753 patent.
[0091] The monoamines have only one amine functionality whereas the
polyamines have two or more. The amines can be primary, secondary
or tertiary amines. The primary amines are characterized by the
presence of at least one --NH.sub.2 group; the secondary by the
presence of at least one H--N<group. The tertiary amines are
analogous to the primary and secondary amines with the exception
that the hydrogen atoms in the --NH.sub.2 or H--N<groups are
replaced by hydrocarbyl groups. Examples of primary and secondary
monoamines include ethylamine, diethylamine, n-butylamine,
di-n-butylamine, allylamine, isobutylamine, cocoamine,
stearylamine, laurylamine, methyllaurtylamine, oleylamine,
N-methylocylamine, dodecylamine, and octadecylamine. Suitable
examples of tertiary monoamines include trimethylamine,
triethylamine, tripropyl amine, tributylamine, monomethyldimethyl
amine, monoethyldimethylamine, dimethylpropyl amine, dimethylbutyl
amine, dimethylpentyl amine, dimethylhexyl amine, dimethylheptyl
amine, and dimethyloctyl amine.
[0092] In one embodiment, the amines (C)(II) are hydroxyamines.
These hydroxyamines can be primary, secondary, or tertiary amines.
Typically, the hydroxamines are primary, secondary or tertiary
alkanolamines, or mixture thereof.
[0093] Such amines can be represented, respectfully, by the
formulae: 15
[0094] and mixtures of two or more thereof; wherein in the above
formulae each R is independently a hydrocarbyl group of 1 to about
8 carbon atoms, or a hydroxyl-substituted hydrocarbyl group of 2 to
about 8 carbon atoms and each R' independently is a hydrocarbylene
(i.e., a divalent hydrocarbyl) group of 2 to about 18 carbon atoms.
The group--R'--OH in such formulae represents the
hydroxyl-substituted hydrocarbylene group. R' can be an acyclic,
alicyclic, or aromatic group. Typically, R' is an acyclic straight
or branched alkylene group such as ethylene, 1,2-propylene,
1,2-butylene, 1,2-octadecylene, etc. group. When two R groups are
present in the same molecule they can be joined by a direct
carbon-to-carbon bond or through a heteroatom (e.g., oxygen,
nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring
structure. Examples of such heterocyclic amines include N-(hydroxyl
lower alkyl)-morpholines, -thiomorpholines, -piperidines,
-oxazolidines, -thiazolidines and the like. Typically, however,
each R is independently a lower alkyl group of up to seven carbon
atoms.
[0095] Suitable examples of the above hydroxyamines include mono-,
di-, and triethanolamine, dimethylethanolamine
(N,N-dimethylethanoloamine), diethylethanol-amine,
(N,N-diethylethanolamine), di-(3-hydroxyl propyl) amine,
N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine and
N,N-di-(2-hydroxyl propyl) amine.
[0096] Preparation of carboxylic acids from corresponding succinic
anhydrides.
[0097] In the preferred embodiment, the acylating agents (C)(I) and
(C)(II) are carboxylic acids. If either or both of carboxylic acids
(C)(I) and (C)(II) are polycarboxylic acids, those acids can be
derived from the corresponding succinic anhydrides by a hydrolysis
reaction with water such that the succinic acids are the major
products. A minor amount of the succinic anhydride may remain
unreacted. Typically, one or more of components (C)(I) and one or
more of components (C)(II) are mixed together with an appropriate
amount of water (1 equivalent to 10 equivalents, more preferably 1
equivalent to 3 equivalents), and heated to a temperature in the
range of from about 20.degree. C. to about 100.degree. C.,
preferably from about 50.degree. C. to about 95.degree. C., more
preferably 80.degree. C. to 95.degree. C.; optionally in the
presence of a normally liquid, substantially inert organic liquid
solvent/diluent, until the desired product has formed.
[0098] Reaction of Carboxylic Acids (C)(I) and (C)(II) and the
Amine (C)(III)
[0099] The carboxylic acids (C)(I) and (C)(II) are converted into
amine carboxylate salts by reaction with ammonia, amine (C)(III),
or mixtures thereof. In one embodiment, (C)(III) is a
hydroxylamine. In one embodiment, 0.5 to 3.0 equivalents of amine
is charged per one acid group of (C)(I) or (C)(II) in preparing the
desired salts. More preferably, the amine is charged at 0.5 to 2.0
equivalents per acid group, more preferably, the amine is charged
at 0.8 to 1.2 equivalents per acid group. This reaction is carried
out at temperatures from about 0.degree. C. to about 100.degree.
C., more preferably from about 20.degree. C. to about 60.degree. C.
Typically the ingredients (the acids and the amine(s)) are mixed
together at room temperature with no external heating.
[0100] In the disclosed invention, the acylating agent (C)(I) is a
succinic acid, and it is reacted with water to prepare a
poly(isobutenyl)-substituted succinic acid. In one embodiment the
polyisobutylene succinic acid or anhydride has a molecular weight
in the range of about 1000 Mn to about 10,000 Mn, and in another
embodiment about 1000 Mn to about 5000 Mn, and in another
embodiment about 1500 Mn to about 3000 Mn. This poly(isobutenyl)
succinic acid is then reacted with an amine. Preferred amines
include but are not limited to alkanolamines and the like. A
preferred alkanolamine is diethylamino ethanol. This reaction gives
a product that is a disalt, also described as a succinate salt. In
the preferred embodiment, the emulsifier is prepared by charging
from about 0.2 to about 3.0 eq amine per equivalent of carboxylic
acid, more preferred about 0.5 to about 2.0 eq amine per equivalent
of carboxylic acid, and more preferred about 0.8 to about 1.2 eq
amine per equivalent carboxylic acid.
[0101] In one embodiment, component (C)(II) is made by reacting an
oleic acid with N,N-diethylamino ethanol in a molar ratio of about
0.2 to about 3.0 eq amine per equivalent of carboxylic acid, more
preferred about 0.5 to about 2.0 eq amine per equivalent of
carboxylic acid, and more preferred about 0.8 to about 1.2 eq amine
per equivalent carboxylic acid. This reaction product is a
carboxylate salt.
[0102] The Water-Soluble Salt (D)
[0103] Another component of the present composition is a
water-soluble, ashless (i.e. metal-free), halogen-, boron-, and
phosphorus-free amine salt, distinct from component (C). The term
"amine" as used herein includes ammonia. Particularly useful are
the amines or ammonium salts such as ammonium nitrate, ammonium
acetate, methyl ammonium nitrate, methyl ammonium acetate, ethylene
diamine diacetate, urea nitrate, urea, guanidiniumnitrate, and
mixtures thereof.
[0104] In one embodiment, the amine salt (D) is represented by the
formula
k[G(NR.sub.3).sub.y].sup.y+nX.sup.p+ (D-I)
[0105] Wherein in formula (D-I), G is hydrogen, or an organic
neutral radical of 1 to about 8 carbon atoms, and in one embodiment
1 to 2 carbon atoms, having a valence of y; each R independently is
hydrogen or a hydrocarbyl group of 1 to about 10 carbon atoms, and
in one embodiment 1 to about 5 carbon atoms, and in one embodiment
1 to 2 carbon atoms; X.sup.p- is an anion having a valence of p;
and k, y, n and p are independently at least 1, provided that when
G is H, y is 1, and further provided that the sum of the positive
charge ky.sup.+ is equal to the sum of the negative charge
nX.sup.p-, such that the amine salt (D) is electrically neutral. In
one embodiment, (D) is a hydrocarbyl or hydrocarbylene group of 1
to about 5 carbon, and in one embodiment 1 to 2 carbon atoms. In
one embodiment, X.sup.y- is a nitrate ion (y=1); in one embodiment
it is an acetate ion (y=1). Suitable examples of the amine salt
include ammonium nitrate (NH.sub.3.HNO.sub.3), ammonium acetate
(NH.sub.3.HOC(O)CH.sub.3), methylammonium nitrate
(CH.sub.3NH.sub.2.HNO.s- ub.3), methylammonium acetate
(CH.sub.3NH.sub.2.HOOCCH.sub.3), ethylene diamine diacetate
(H.sub.2NCH.sub.2CH.sub.2NH.sub.2.2HOOCCH.sub.3), urea nitrate
(H.sub.2NC(O)NH.sub.2.HNO.sub.3), and urea dintrate
(H.sub.2NC(O)NH.sub.2.2HNO.sub.3).
[0106] As an illustration of formula (D-I), ethylene diamine
diacetate can be written in its ionic form as
[H.sub.3NCH.sub.2CH.sub.2NH.sub.3].sup.2+2CH.sub.3CO.sub.2.sup.-
[0107] In this case, in formula (D-I), G is--CH.sub.2CH.sub.2--; R
is hydrogen; y is 2; n is 2; p is 1; and X.sup.p- is
CH.sub.3CO.sub.2.sup.-
[0108] In one embodiment, the amine salt (D) of the present
composition functions as an emulsion stabilizer, i.e., it acts to
stabilize the present emulsified water-blended fuel composition.
Compositions with the amine salt (D) have longer stability as
emulsions than the compositions without the amine salt (D).
[0109] In one embodiment, the amine salt (D) functions as a
combustion improver. A combustion improver is characterized by its
ability to increase the mass burning rate of water-blended fuel
composition. It is known that the presence of water in fuels
reduces the power output of an internal combustion engine. The
presence of a combustion improver has the effect of improving the
power output of an engine. The improved power output of the engine
can often be seen in a plot of mass burning rate versus crank angle
(which angle corresponds to the number of degrees of revolution of
the crankshaft which is attached to the piston rod, which in turn
is connected to pistons). One such plot is shown in FIG. 2, which
is discussed further under Examples below. The mass burning rate
will be higher for a fuel with a combustion modifier than for a
fuel lacking the combustion modifier. This improved power output
caused by the presence of a combustion improver is to be
distinguished from improvement in ignition delay caused by a cetane
improver. Although some cetane improvers may function as a
combustion improver, and some combustion improvers as cetane
improvers, the actual performance characteristics or effects of
combustion improvement are clearly distinct from improvements in
ignition delay. Improving ignition delay generally relates to
changing the onset of combustion (i.e. they will affect where on
the x-axis of FIG. 1 the peak mass burning rate will occur) whereas
improving the power output relates to improving the peak cylinder
pressure (i.e., the amplitude of the peak mass burning rate on the
y-axis of FIG. 1FIG.)
[0110] The amine salt (D) is present at a level of about 0.001 to
about 15%, in one embodiment from about 0.001 to about 1%, in one
embodiment about 0.05 to about 5%, in one embodiment about 0.5 to
about 3%, and in one embodiment about 1 to about 10% by weight of
the emulsified water-blended fuel composition.
[0111] The Cosurfactants
[0112] In addition to the presence of component (C) as an
emulsifier, the present composition can also contain other
emulsifiers, which may be present as cosurfactants. These
emulsifiers/cosurfactants include but are not limited to ionic or
nonionic compounds, having a hydrophilic lipophilic balance (HLB)
in the range of about 1 to about 40, and in one embodiment about 4
to about 15. Examples of these emulsifiers are disclosed in
McCutcheon's Emulsifiers and Detergents, 1993, North American &
International Edition. Some generic examples include 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 and derivatives, olefin sulfonates, 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 or fatty
esters, sulfonates of dodecyl and tridecyl benzenes or condensed
naphthalenes or petroleum, sulfosuccinates and derivatives, and
tridecyl and dodecyl benzene sulfonic acids.
[0113] In one embodiment, the cosurfactant is a poly(oxyalkene)
compound, and in one embodiment, the polyoxyalkylene compound is a
copolymer of ethylene oxide and propylene oxide copolymer. In one
embodiment, this copolymer is a triblock copolymer represented by
the formula 16
[0114] wherein in formula (E-I), x and x' are the number of repeat
units of propylene oxide and y is the number of repeat units of
ethylene oxide, as shown in the formula. This triblock copolymer is
available from BASF Corporation under the name PLURONIC.TM. R
surfactants. In one embodiment, the triblock copolymer has a number
average molecular weight of about 1800 to about 3000. In one
embodiment, the triblock copolymer has a number average molecular
weight of about 2150, is a liquid at 20.degree. C., having a
melt/pour point of about -25.degree. C., has Brookfield viscosity
of 450 cps, and has surface tensions (25.degree. C.) at 0.1, 0.01,
and 0.001% concentration of about 41.9, 44.7, and 46.0 dynes/cm
respectively. It is available under the name PLURONIC.TM. 17R2. In
one embodiment, the triblock copolymer has a number average
molecular weight of about 2650, is a liquid at 20.degree. C.,
having a melt/pour point of about -18.degree. C., has Brookfield
viscosity of 600 cps, and has surface tensions (25.degree. C.) at
0.1, 0.01, and 0.001% concentration of about 44.1, 44.5, and 51.4
dynes/cm respectively. It is available under the name PLURONIC.TM.
17R4.
[0115] In one embodiment, the poly(oxyalkylene) compound is an
alcohol ethoxylate represented by the formula
RO(CH.sub.2CH.sub.2O).sub.nH wherein R is a hydrocarbyl group of 8
to 30 carbon atoms, and in one embodiment about 8 to about 20, and
in one embodiment about 10 to about 16 carbon atoms; and n ranges
from about 2 to about 100, and in one embodiment about 2 to about
20, and in one embodiment about 2 to about 10. In one embodiment R
is nonylphenyl, and in one embodiment, R is nonylphenyl and n is
about 4. It is available from Rhone-Poulenc, under the name
IGEPAL.TM. CO-430. It has about 44% ethylene oxide, has an HLB
value of about 8.8. It is an aromatic odor, is pale yellow liquid,
having a density at 25.degree. C. of 1.02, viscosities at
25.degree. C. and 100.degree. C. of about (160-260) and (8-10)
respectively;
[0116] solidification point of -21 to 2; and a pour point of --16
to 2.degree. F. In one embodiment, R is nonylphenyl and n is about
6. It is available from Rhone-Poulenc, under the name IGEPAL.TM.
CO-530. It has about 54% ethylene oxide, has an HLB value of about
10.8. It is an aromatic odor, is pale yellow liquid, having a
density at 25.degree. C. of 1.04, viscosities at 25.degree. C. and
100.degree. C. of about (180-280) and (10-12) respectively;
solidification point of --23 to 2.degree. F.; and a pour point of
--18 to 2.degree. F.
[0117] In one embodiment, R in the above alcohol ethoxylate is a
linear C.sub.9-11 alkyl group and n ranges from about 2 to about
10, and in one embodiment from about 2 to about 6. These alcohol
ethoxylates are available from Shell International Petroleum
Company under the name NEODOL.TM. alcohol ethoxylates. In one
embodiment, n is about 2.7. It is available under the name
NEODOL.TM. 91-2.5. It has a number average molecular weight of
about 281, an ethylene oxide content of about 42.3% by weight, a
melting range of about -31 to -2F, a specific gravity (77.degree.
F.) of about 0.925, viscosity at 100.degree. F. of about 12cSt, a
hydroxyl number of about 200 mg KOH/g, and an HLB number of about
8.5. In one embodiment, n is about 8.2. It is available under the
name NEODOL 91-8. It has a number average molecular weight of about
519, an ethylene oxide content of about 69.5% by weight, a melting
range of about 45.degree. F. to 68.degree. F., a specific gravity
(77.degree. F.) of about 1.008, viscosity at 100.degree. F. of
about 39 cSt, a hydroxyl number of about 108 mg KOH/g, and an HLB
number of about 8.5.
[0118] In one embodiment the cosurfactant comprises at least one
sorbitan ester.
[0119] The sorbitan esters include sorbitan fatty acid esters
wherein the fatty acid component of the ester comprises a
carboxylic acid of about 10 to about 100 carbon atoms, and in one
embodiment about 12 to about 24 carbon atoms. Sorbitan is a mixture
of anhydrosorbitols, principally 1,4-sorbitan and isosorbide:
17
[0120] Sorbitan, (also known as monoanhydrosorbitol, or sorbitol
anhydride) is a generic name for anhydrides derivable from sorbitol
by removal of one molecule of water. The sorbitan fatty acid esters
of this invention are a mixture of partial esters of sorbitol and
its anhydrides with fatty acids. These sorbitan esters can be
represented by the structure below which may be any one of a
monoester, diester, triester, tetraester, or mixtures thereof.
18
[0121] In formula (E-III), each Z independently denotes a hydrogen
atom or C(O)R--, and each R mutually independently denotes a
hydrocarbyl group of about 9 to about 99 carbon atoms, more
preferably about 11 to about 23 carbon atoms. Examples of sorbitan
esters include sorbitan stearates and sorbitan oleates, such as
sorbitan stearate (i.e., monostearate), sorbitan distearate,
sorbitan tristearate, sorbitan monooleate and sorbitan
sesquioleate. Sorbitan esters are available commercially under the
names Spans.TM. and Arlacels.TM. from ICI.
[0122] The sorbitan esters also include polyoxyalkylene sorbitan
esters wherein the alkylene group has about 2 to about 30 carbon
atoms. These polyoxyalkylene sorbitan esters can be represented by
the structure 19
[0123] wherein in formula (E-IV), each R independently is an
alkylene group of about 2 to about 30 carbon atoms; R.sup.1 is a
hydrocarbyl group of about 9 to about 99 carbon atoms, more
preferably about 11 to about 23 carbon atoms; and w, x, y and z
represent the number of repeat oxyalkylene units. For example
ethoxylation of sorbitan fatty acid esters leads to a series of
more hydrophilic surfactants, which is the result of hydroxy groups
of sorbitan reacting with ethylene oxide. One principal commercial
class of these ethoxylated sorbitan esters are those containing
about 2 to about 80 ethylene oxide units, and in one embodiment
from about 2 to about 30 ethylene oxide units, and in one
embodiment about 4, in one embodiment about 5, and in one
embodiment about 20 ethylene oxide units. They are available from
Calgene Chemical under the name POLYSORBATE.TM. and from ICI under
the name TWEEN.TM.. Typical examples are polyoxyethylene
(hereinafter "POE") (20) sorbitan tristearate (Polysorbate 65;
Tween 65), POE (4) sorbitan monostearate (Polysorbate 61; Tween
61), POE (20) sorbitan trioleate (Polysorbate 85; Tween 85), POE
(5) sorbitan monooleate (Polysorbate 81; Tween 81), and POE (80)
sorbitan monooleate (Polysorbate 80; Tween 80). As used in this
terminology, the number within the parentheses refers to the number
of ethylene oxide units present in the composition.
[0124] In one embodiment, the cosurfactant comprises at least one
fatty acid diethanolamide.
[0125] The fatty acid diethanolamides are 1:1 fatty acid
diethanolamides made by reacting a fatty acid with diethanolamide
in a 1:1 mole ratio under amide forming conditions. These 1:1 fatty
acid diethanolamides are available from Witco Corporation under the
name SCHERCOMID.TM.. The fatty acids used to make these 1:1 fatty
acid diethanlomides may be monocarboxylic fatty acids or they may
be derived from natural oils (such as triglycerides). Useful fatty
acids and their sources include lauric acid, myristic acid, coconut
acid, coconut oil, oleic acid, tall oil fatty acid, linoleic acid,
soybean oil, apricot kernel oil, wheat germ oil, and mixtures
thereof. In one embodiment, the fatty acid diethanolamide is
derived from oleic acid. It is available commercially under the
name SCHERCOMID.TM. SO-A also referred to as Oleamide DEA. It is a
clear amber liquid, has a maximum acid value of about 5, an alkali
value of about 40-60, and contains a minimum of 85% amide.
[0126] The cosurfactant when present is present in an emulsifying
amount, i.e., it is present in a quantity sufficient to maintain
the present composition as an emulsion. In one embodiment, it is
present at a level of about 0.005 to about 20%, and in one
embodiment from about 0.005 to about 10%, and in one embodiment
from about 0.005 to about 1%.
[0127] The Organic Nitrate Cetane Improver
[0128] In one embodiment of the present invention, the present
composition further comprises at least one organic cetane improver.
The organic nitrate cetane improver includes nitrate esters of
substituted or unsubstituted aliphatic or cycloaliphatic alcohols
which may be monohydric or polyhydric. Preferred organic nitrates
are substituted or unsubstituted alkyl or cycloalkyl nitrates
having up to about 10 carbon atoms, preferably from 2 to about 10
carbon atoms. The alkyl group may be either linear or branched, or
a mixture of linear or branched alkyl groups. Specific examples of
nitrate compounds suitable for use in the present invention include
methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate,
allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl
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 suitable 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. While not
particularly preferred, the nitrate esters of higher alcohol may
also be useful. Such higher alcohols tend to contain more than
about 10 carbon atoms. Preferred are the alkyl nitrates having from
about 5 to about 10 carbon atoms, most especially mixtures of
primary amyl nitrates, mixtures of primary hexyl nitrates, and
octyl nitrates such as 2-ethylhexyl nitrate.
[0129] The concentration of the organic nitrate cetane improver in
the present composition can be any concentration sufficient to
counteract the reduction in cetane number caused by the addition of
water in the present water-blended fuel compositions. Generally,
addition of water to fuel acts to lower the cetane number of the
fuel. As a general rule of thumb, the cetane number of fuel goes
down by 1/2 unit per each 1% addition of water. Lowering of cetane
number results in ignition delay, which can be counteracted by the
addition of cetane enhancers/improvers. Generally, the amount of
organic nitrate cetane improver ester will fall in the range of
about 0.05% to about 10% and in one embodiment about 0.05% to about
1% by weight of the water-blended fuel composition.
[0130] The Alcohol/Antifreeze
[0131] In one embodiment of the present invention, the composition
further comprises an alcohol. The alcohol is generally an
antifreeze agent but may also be a cosolvent or combinations of
both. Examples of suitable alcohols and their isomers include, but
are not limited to ethylene glycol, propylene glycol, methanol,
ethanol, glycerol, isopropanol, octanol, butanol, pentanol,
hexanol, heptanol, 4-ethoxy butanol and combinations thereof.
[0132] The antifreeze can be present at any concentration
sufficient to keep the present composition from freezing within the
operable temperature range. In one embodiment, it is present at a
level of about 0.01% to about 10%, and in one embodiment, about
0.1% to 5% by weight of the water-blended fuel composition.
[0133] Specific Embodiment
[0134] The following examples demonstrate the advantages of the
present invention.
EXAMPLE 1
[0135] Preparation of PIB Succinic Acid
[0136] A 2300 Mn poly(isobutenyl) succinic anhydride (about 9410g,
about 6.84 eq C=O) was charged to a 12-liter spherical 4-neck flask
equipped with a temperature controller regulating a rheostated
heating mantle and a thermocouple in a glass thermowell. The
material was stirred at about 45.degree. C. and an above-surface
N.sub.2 sweep was set at about 1 SCFH (standard cubic feet per
hour). The mixture was heated to about 90.degree. C. Deionized
water (about 184.8g, about 20.54 equivalents) was then added over
about 10 minutes. The mixture was heated at about 90.degree. C. for
about 2 hours. Infrared analysis showed acid peak at 1714
cm-.sup.1- with a slight anhydride or lactone shoulder at 1786
cm-.sup.-. The mixture was cooled to about 50.degree. C. and
discharged.
EXAMPLE 2
Simultaneous Preparation of Both Salts.
[0137] Oleic acid (about 2450g), 2-ethyl hexyl nitrate (about
3420g), and hydrolyzed 2300 molecular weight PIBSA (about 2410 g,
about 50% active chemical by weight) (from Example 1) was charged
to a 12-liter spherical 4-neck flask equipped with a temperature
controller monitoring a thermocouple in a glass thermowell. The
mixture was stirred at room temperature under a nitrogen flow at
about 1 SCFH, and the materials were mixed until homogeneous.
Diethylamino ethanol (about 1110 g) was charged over 1 hour, and a
mild exotherm was observed. The resulting material was a solution
of carboxylate salts in 2-ethylhexyl nitrate.
[0138] Some illustrative water-blended fuel compositions within the
scope of the invention are disclosed Table 1. The amounts are in
parts by weight.
1TABLE I Components Emulsion A Emulsion B Emulsion C Diesel Fuel
77.80 77.51 75.30 Water 20.00 20.00 16.80 Surfactant 1.sup.1 0.526
1.16 0.526 (.about.59% active) Surfactant 2.sup.2 0.724 0.382 0.724
2-ethyl hexyl nitrate 0.714 0.714 0.714 Ammonium nitrate 0.12 0.12
0.12 Propylene glycol 0.12 0.12 0.12 Methanol 0 0 5.70 .sup.1This
is a biscarboxylate salt that is made by reaction of hydrolyzed
2300 molecular weight PIBSA with diethyl ethanolamine. .sup.2This
is a carboxylate salt that is made by reacting oleic acid with
diethyl ethanolamine.
[0139] The emulsions have a milky white appearance. The stability
of the emulsion is determined visually by tracking percentage of
water-blended fuel composition remaining as a white emulsion at
room temperature four weeks after preparation. The percentage of
white emulsion and free oil is indicated in the table below:
2 Components Emulsion A Emulsion B Emulsion C Free oil 7 9 13 White
emulsion 93 91 87
[0140] As a point of reference, a baseline surfactant system gives
>10% oil and <90% white emulsions after 4 weeks at room
temperature. This is illustrative of concentrates that can be used
to make the
[0141] water-blended fuel compositions of the invention. The
numerical values indicated below are parts by weight.
3 Components Concentrate A Concentrate B PIB succinic acid.sup.1
21.94 41.48 Oleic acid 22.24 10.52 Diethylamino ethanol 10.11 6.95
2-ethyl hexyl nitrate 31.04 27.049 54% aqueous ammonium 9.66 8.56
nitrate Propylene glycol 5.00 5.00 .sup.1derived from 2300
molecular weight PIBSA
[0142] This demonstrates that the emulsified water-blended fuel
compositions using the concentrates disclosed above. In the table
below, all numerical values are in parts by weight.
4 Components Emulsion A Emulsion B Diesel Fuel 79-81 79-81 Water
18-20 18-20 Concentrate A 1.5-3.0 -- Concentrate B -- 1.5-3.0
[0143] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *