U.S. patent application number 10/492731 was filed with the patent office on 2004-12-02 for combustion modifiers for water-blended fuels.
Invention is credited to Baker, Mark R, Daly, Daniel T, Langer, Deborah A, Wolak, Thomas J.
Application Number | 20040237383 10/492731 |
Document ID | / |
Family ID | 27402459 |
Filed Date | 2004-12-02 |
United States Patent
Application |
20040237383 |
Kind Code |
A1 |
Daly, Daniel T ; et
al. |
December 2, 2004 |
Combustion modifiers for water-blended fuels
Abstract
A combustion modifier for an aqueous hydrocarbon fuel emulsion
that reduces nitrogen oxides (NOx), hydrocarbons, carbon monoxide
(CO) and particulate matter from the emissions of internal
combustion engines. A class of combustion modifiers used in this
invention contain nitrogen. The nitrogen-containing combustion
modifiers are nitro compounds, hydroxylamines or salts thereof,
nitrogen compounds having at least one strained ring group
containing from 3 to 5 ring atoms, nitrites, nitramines and
mixtures thereof. The non nitrogen-containing combustion modifier
comprises compounds containing at least one strained ring
compound.
Inventors: |
Daly, Daniel T; (Solon,
OH) ; Langer, Deborah A; (Chesterland, OH) ;
Baker, Mark R; (Lyndhurst, OH) ; Wolak, Thomas J;
(Mentor, OH) |
Correspondence
Address: |
The Lubrizol Corporation
Petent Dept-Mail Drop 022B
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Family ID: |
27402459 |
Appl. No.: |
10/492731 |
Filed: |
March 25, 2004 |
PCT Filed: |
February 28, 2002 |
PCT NO: |
PCT/US02/06110 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60272209 |
Feb 28, 2001 |
|
|
|
60317222 |
Sep 5, 2001 |
|
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|
60317205 |
Sep 5, 2001 |
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Current U.S.
Class: |
44/301 |
Current CPC
Class: |
C10L 1/1608 20130101;
C10L 1/1855 20130101; C10L 1/1881 20130101; C10L 1/1966 20130101;
C10L 1/2222 20130101; C10L 1/2366 20130101; C10L 1/198 20130101;
C10L 1/226 20130101; C10L 1/328 20130101; C10L 1/1826 20130101;
C10L 1/2283 20130101; C10L 1/23 20130101; C10L 1/245 20130101; C10L
1/1985 20130101; C10L 1/1883 20130101; C10L 1/2364 20130101; C10L
1/125 20130101; C10L 1/2437 20130101; C10L 1/1852 20130101; C10L
1/2383 20130101; C10L 1/1824 20130101; C10L 1/231 20130101; C10L
1/232 20130101; C10L 1/2443 20130101; C10L 10/02 20130101; C10L
1/221 20130101; C10L 1/10 20130101; C10L 1/2456 20130101; C10L
1/1266 20130101; C10L 1/1963 20130101; C10L 1/2225 20130101; C10L
1/238 20130101; C10L 1/224 20130101 |
Class at
Publication: |
044/301 |
International
Class: |
C10L 001/32 |
Claims
What is claimed is:
1. An aqueous hydrocarbon fuel emulsion comprising, a liquid
hydrocarbon fuel, water, at least one emulsifier and a nitrogen
containing combustion modifier, wherein the nitrogen containing
combustion modifier comprises: (a) a nitro compound; (b) a
hydroxylamine or a salt thereof wherein each hydroxylamino group of
the hydroxylamine or salt thereof contains no more than one
tertiary substituent; (c) a compound having at least one strained
ring group containing from 3 to 5 ring atoms; (d) organic nitrites;
(e) nitramines; and (f) mixtures thereof.
2. The fuel composition of claim 1 comprising a hydroxylamine
wherein the hydroxylamine has the general formula 9wherein each
R.sub.a and R.sub.b is, independently, a member selected from the
group consisting of H, a primary hydrocarbyl group and a secondary
hydrocarbyl group containing from 1 to about 25 carbon atoms, and n
ranges from 1 to about 30.
3. The fuel composition of claim 1 comprising a hydroxylamine
wherein the hydroxylamine has the general formula 10wherein each
R.sub.c is, independently, H or a hydrocarbyl group, each R.sub.d
is, independently, a lower alkylene group and x ranges from 1 to
about 29.
4. The fuel composition of claim 1 comprising a hydroxylamine salt
and wherein the salt is at least one member of the group consisting
of nitrates, sulfates, sulfonates, carbonates and carboxylates.
5. The fuel composition of claim 1 wherein the nitro compounds are
selected from the group consisting of aliphatic and aromatic nitro
compounds.
6. The fuel composition of claim 1 wherein the nitro compound
comprises at least one member of the group consisting of
nitromethane, dinitrobutyl phenol, dinitropropane, nitromethane,
nitropropane, trinitrotoluene, dinitrotoluene, 1,2-dinitropropanol
and hydroxymethyl nitropropane.
7. The fuel composition of claim 1 wherein the ring group is a
hydrocarbyl group substantially free of heteroatoms.
8. The fuel composition of claim 1 wherein the ring contains both
carbon atoms and heteroatoms, said heteroatoms being selected from
the group consisting of O, S and N.
9. The fuel composition of claim 7 wherein the ring contains at
least two carbon atoms.
10. The fuel composition of claim 9 wherein the ring contains no
more than 2 heteroatoms.
11. The fuel composition of claim 7 wherein the hydrocarbyl group
is a cyclopropyl group, a cyclobutyl group or a cyclopentyl
group.
12. The composition of claim 10 wherein the ring is an epoxy group,
an oxetane group or a furan group.
13. The fuel composition of claim 1 wherein the compound comprises
at least two strained ring groups.
14. The fuel composition of claim 11 wherein the compound comprises
cyclopropyl methanol, cyclobutyl amine and cyclobutyl
hydroxylamine.
15. The fuel composition of claim 12 wherein the compound is
selected from the group consisting of 3,3-dimethyloxetane,
1-methoxy-2-methylpropylene oxide and
2,5-dimethoxytetrahydrofuran.
16. The fuel composition of claim 1 further comprising at least one
component selected from the group consisting of (a) dispersants,
(b) lubricity agents, (c) cold flow improvers, (d) fluidizers, (e)
surfactants, (f) corrosion inhibitors and (g) mixtures thereof.
17. The fuel composition of claim 1 comprising a nitramine selected
from the group consisting of benzyl nitramine, phenyl nitramine,
methyl nitramine 2-propyl nitramine, ammonium dinitramine, ethylene
dinitramine and combinations thereof.
18. A method from improving the combustion characteristics of an
aqueous hydrocarbon fuel emulsion comprising incorporating therein
a combustion improving amount of a nitrogen containing combustion
improver selected from the group comprising: (a) a nitro compound;
(b) a hydroxylamine or a salt thereof wherein each hydroxylamino
group of the hydroxylamine or salt thereof contains no more than
one tertiary substituent; (c) a compound having at least one
strained ring group containing from 3 to 5 ring atoms; (d) organic
nitrites; (e) nitramines; and (f) mixtures thereof.
19. The method of claim 18 wherein the improved combustion
characteristics comprise at least one of reduced particulate
emissions, reduced NO.sub.x emissions, reduce carbon monoxide
emissions reduced hydrocarbon emissions or combinations
thereof.
20. A method for operating an internal combustion engine comprising
providing to the combustion chamber of said engine during operation
thereof, the fuel composition of claim 1.
21. An aqueous hydrocarbon fuel emulsion comprising, a liquid
hydrocarbon fuel, water, at least one emulsifier and a non-nitrogen
containing combustion modifier containing at least one strained
ring compound.
Description
[0001] This is filed from U.S. provisional application Ser. No.
60/272,209, filed Feb. 28, 2001, and U.S. provisional application
Ser. No. 60/317,222, filed Sep. 5, 2001, and U.S. provisional
application Ser. No. 60/317,205, filed Sep. 5, 2001.
TECHNICAL FIELD
[0002] The invention relates to combustion improving additives for
aqueous hydrocarbon fuel emulsions. More particularly, the
invention relates to combustion modifiers for aqueous hydrocarbon
fuel emulsions that reduces nitrogen oxides (NOx), hydrocarbons
(HC), carbon monoxide (CO) and particulate matter (PM) from the
emissions of internal combustion engines.
BACKGROUND OF THE INVENTION
[0003] Internal combustion engines, especially diesel engines, that
employ water mixed with the fuel in the combustion chamber can
produce lower nitrogen oxides, hydrocarbons and particulate
emissions per unit of power output. The reduction of harmful
emissions is an environmental issue because the emissions
contribute to smog and air pollution. Governmental regulations and
environmental concerns have driven the need to reduce harmful
emissions from engines.
[0004] Water is inert toward combustion and lowers the peak
combustion temperature resulting in reduced particulates and NOx
formation. Water-blended fuels are being employed to reduce NOx and
particulate matter emissions from internal combustion engines. It
would be advantageous to improve the efficiency and utilization of
aqueous hydrocarbon fuels and further reduce the harmful emissions
of such fuels by also reducing hydrocarbons and carbon monoxide
emissions.
[0005] U.S. Pat. No. 5,591,237 discloses a fuel additive
concentrate package comprising detergent/dispersent, an organic
nitrate combustion improver and a corrosion inhibitor such as
nitric acid/hydrochloric acid to provide enhanced shelf-life
ability.
[0006] U.S. Pat. No. 5,669,938 discloses a fuel composition which
comprises a water in oil emulsion comprising hydrocarbonaceous
middle distillate fuel, water and an emission reducing amount of at
least one fuel soluble organic nitrate ignition improver such as
2-ethylhexyl nitrate providing reduction of exhaust emissions from
diesel engines.
[0007] Combustion improvers of this invention improve the
combustion characteristics of aqueous hydrocarbon fuels. The
improved combustion characteristics include reduced NOx emissions,
reduced CO emissions, reduced hydrocarbon emissions and reduced
particulate matter emissions, as well as greater power output which
can be expressed as an improved fuel efficiency.
[0008] The term "NOx" 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 "aqueous hydrocarbon fuel emulsion" and "water
fuel emulsion" and "aqueous hydrocarbon fuel" and "water fuel
blend" are interchangeable.
SUMMARY OF THE INVENTION
[0009] This invention relates to an aqueous hydrocarbon fuel
emulsion comprising, a liquid hydrocarbon based fuel, water, at
least one emulsifier and a combustion modifier. A class of
combustion modifiers used in this invention contain nitrogen. The
nitrogen-containing combustion modifier comprises:
[0010] (a) a nitro compound;
[0011] (b) a hydroxylamine or a salt thereof wherein each
hydroxylamino group of the hydroxylamine or salt thereof contains
no more than one tertiary substituent;
[0012] (c) a nitrogen compound having at least one strained ring
group containing from 3 to 5 ring atoms;
[0013] (d) organic nitrites;
[0014] (e) nitramines; and
[0015] (f) mixtures thereof.
[0016] The non nitrogen-containing combustion modifier comprises
compounds containing at least one strained ring compound.
[0017] The invention is further directed to a method for improving
the combustion characteristics of an aqueous hydrocarbon fuel
comprising incorporating a combustion improving amount of a
nitrogen containing compound in the fuel wherein the nitrogen
containing compound comprises:
[0018] (a) a nitro compound;
[0019] (b) a hydroxylamine or a salt thereof wherein each
hydroxylamino group of the hydroxylamine or salt thereof contains
no more than one tertiary substituent;
[0020] (c) a nitrogen compound having at least one strained ring
group containing from 3 to 5 ring atoms;
[0021] (d) organic nitrites;
[0022] (e) nitramines; and
[0023] (f) mixtures thereof.
[0024] The non nitrogen-containing combustion modifier comprises
compounds containing at least one strained ring compound
DETAILED DESCRIPTION OF THE INVENTION
[0025] The aqueous hydrocarbon fuel emulsion composition of this
invention comprises at least compound which acts as a combustion
improver. The nitrogen containing combustion improver compounds are
selected from the group consisting of:
[0026] (a) a nitro compound;
[0027] (b) a hydroxylamine or a salt thereof wherein each
hydroxylamino group of the hydroxylamine or salt thereof contains
no more than one tertiary substituents;
[0028] (c) a nitrogen compound having at least one strained ring
group containing from 3 to 5 ring atoms;
[0029] (d) organic nitrites;
[0030] (e) nitramines; and
[0031] (f) mixtures thereof.
[0032] The non nitrogen-containing combustion modifier comprises of
compounds containing at least one strained ring compound
[0033] The preferred nitrogen containing combustion improver
compound is hydroxy ammonium nitrate (HAN).
[0034] The nitrogen containing compounds are used in the amount
ranging in one embodiment from about 0.01 to about 5 percent per
weight, in one embodiment from about 0.02 to about 2 percent per
weight, in one embodiment from about 0.04 to about 1.5 per weight,
and in one embodiment from about 0.05 to about 1.0 per weight of
the aqueous hydrocarbon fuel emulsion.
[0035] Suitable emulsifiers comprise:
[0036] (i) at least one fuel-soluble product made by reacting at
least one hydrocarbyl-substituted carboxylic acid acylating agent
with ammonia or an amine, the hydrocarbyl substituent of said
acylating agent having about 50 to about 500 carbon atoms;
[0037] (ii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0038] (iii) a mixture of (ii) with (i);
[0039] (iv) 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;
[0040] (v) the reaction product of polyacidic polymer with at least
one fuel soluble product made by reacting at least one
hydrocarbyl-substiutted carboxylic acid acylating agent with
ammonia, an amine, a polyamine, alkanol amine, or hydroxy
amines;
[0041] (vi) an amino alkylphenol which is made by reacting an
alkylphenol, an aldehyde and an amine resulting in an amino
alkylphenol, or
[0042] (vii) the combination of (vi) and (i), (ii), (iii), (iv),
(v) or combination thereof.
[0043] Hydroxylamines and Salts Thereof
[0044] The hydroxylamine or a salt thereof is a combustion modifier
for the aqueous hydrocarbon fuel. The hydroxylamine or salt thereof
can be a hydroxylamino group of the hydroxylamine or salt thereof
containing no more than one tertiary alkyl substituent.
[0045] In one embodiment the hydroxylamine has the general formula
1
[0046] wherein each of R.sub.a and R.sub.b is, independently, a
member selected from the group consisting of H, a primary
hydrocarbyl group and a secondary hydrocarbyl group, particularly,
H or a hydrocarbyl group containing from 1 to about 25 carbon
atoms, and especially a lower alkyl group, and n ranges from 1 to
about 30, preferably, from 1 to about 4, and most preferably, 1. Of
course, it is obvious that when R.sub.a is H, then n equals 1.
[0047] Particularly preferred is where each hydrocarbyl group is,
independently, a primary alkyl group, especially one containing
from 1 to about 6 carbon atoms.
[0048] In another embodiment, the hydroxylamine has the general
formula 2
[0049] wherein each R.sub.c is, independently, H or a hydrocarbyl
group, particularly, H or a lower alkyl group, each R.sub.d is,
independently, a lower alkylene group, preferably an ethylene or
propylene group, most preferably, an ethylene group, and x ranges
from 1 to about 29, preferably, from 1 to about 5. In another
embodiment the general formula above has at least one of the N with
an Rc group substituted for the OH group.
[0050] Methods for preparing hydroxylamines are known in the
art.
[0051] In another preferred embodiment, the combustion modifiers
comprises a hydroxylamine salt. Hydroxylamines from which the
hydroxylamine salts are derived are the same as the hydroxylamines
described hereinabove. Typically, the salt is at least one member
of the group consisting of nitrates, sulfates, sulfonates,
carbonates and carboxylates. Nitrates and carbonates are preferred
with nitrates being particularly preferred. The salts are generally
obtained by contacting a hydroxylamine with an appropriate acid,
optionally, in the presence of a diluent. Many of these salts are
commercially available, for example, from chemical supply houses
such as Aldrich Chemical Company, Milwaukee, Wis., USA.
[0052] Nitro Compounds
[0053] At least one nitro compound hydrocarbon fuel can be used as
a combustion modifier for the aqueous hydrocarbon fuel. The nitro
compounds can be aliphatic or aromatic and may be mono- or
polynitro-compounds. Polynitro compounds are preferred. Useful
nitro compounds include purely hydrocarbon and substituted
hydrocarbon nitro compounds. Examples of aromatic nitro compounds
include nitrobenzene, dinitrotoluene, trinitrotoluene, nitrated
phenols, for example butyl-dinitrophenol, and aliphatic compounds,
preferably alkyl compounds, including substituted alkyl compounds,
preferably purely alkyl compounds and more preferably, lower alkyl
compounds. Examples include nitromethane, nitropropane,
dinitropropane, hydroxymethyl nitropropane,
1,3-dimorpholino-2-nitropropa- ne, 1,2-dinitropropane,
2-methyl-2-nitropropane, bis(2-nitropropyl)methane and the
like.
[0054] Compounds Containing Strained Ring
[0055] At least one compound having at least one strained ring
group containing from 3 to 5 ring atoms can be used as a combustion
modifier for the aqueous hydrocarbon fuel. The compounds can be
monocyclic or polycyclic compounds, having fused ring systems
and/or ring systems connected directly or via a bridge group,
and/or spiro-compounds which polycyclic compounds have, for
example, from two to four rings and which are unsubstituted or
substituted and can contain heteroatoms (such as, for example, O,
S, or N in one or more rings and/or can contain fused thereto
aromatic or heteroaromatic rings, for example o-phenylene,
o-naphthylene, o-pyridinylene or o-pyrirnidinylene. The individual
strained cyclic rings contain from 3 to 5, preferably 3 to 4, more
often 3, ring members. These include cyclopropyl groups, cyclobutyl
groups and cyclopentyl groups as well as heteroatom-containing
analogues thereof.
[0056] As defined herein, `strained ring` compounds include 3 and 4
membered rings containing olefinic unsaturation, but do not include
olefinically unsaturated 5-membered rings. Preferably, the strained
ring compounds used in this invention are substantially saturated
and most preferably are free of olefinic unsaturation.
`Substantially saturated` means no more than 5% of the strained
ring compounds contain ring unsaturated bonds. The expression `free
of olefinic unsaturation` means the strained ring compounds contain
no more than an impurity amount of unsaturated ring components.
[0057] In one embodiment, the ring group is a hydrocarbyl group
substantially free of heteroatoms. Examples include cyclopropyl
methanol, cyclobutyl amine and cyclobutyl hydroxylamine.
[0058] In another embodiment, the ring contains one or more
heteroatoms as mentioned hereinabove. Such heteroatom containing
compounds may be illustrated by, for example, furans, dioxolanes,
oxetanes, epoxides, aziridines, and thio-analogues thereof and
compounds containing one or more of these groups.
[0059] Heterocyclic ring groups contain at least 2 carbon atoms and
preferably no more than 2 heteroatoms, often but one
heteroatom.
[0060] Preferred heteroatoms are oxygen and nitrogen, although
compounds containing sulfur heteroatoms are also useful. Examples
of preferred oxygen containing compounds or groups are dioxolane,
epoxide, oxetane and furan. Specific examples include
3,3-dimethyloxetane, 1-methoxy-2-methylpropylene oxide,
2-methoxydioxolane and 2,5-dimethoxytetrahydrofuran, preferably,
3,3-dimethyloxetane
[0061] As noted hereinabove, the compound may contain more than one
strained ring group, which groups may be present as fused, linked,
Spiro- etc groups. Preferably, such compounds contain 2 strained
ring groups.
[0062] In one preferred embodiment, the compounds containing two or
more strained ring groups are substantially free of heteroatoms.
Examples include dicyclopropyl ketone, dicyclobutyl ketone and
compounds of the formula 3
[0063] The strained ring group containing compound is typically
used in amounts ranging from about 50 to about 50,000 parts by
weight per million parts by weight (ppm) of fuel, more often from
about 500 to about 20,000 ppm, typically about 5,000 ppm and in
another embodiment, about 2500 ppm.
[0064] Nitrites
[0065] The nitrites are combustion modifiers for the aqueous
hydrocarbon fuel. At least one nitrite compound can be used as a
combustion modifier for the aqueous hydrocarbon fuel. The nitrite
compounds can be aliphatic or aromatic and may be mono- or
polynitrite compounds or combinations thereof. Polynitrite
compounds are preferred. Useful nitrite compounds include but are
not limited too purely hydrocarbon and substituted hydrocarbon
nitrite compounds or combinations thereof. Examples of aromatic
nitrite compounds include but ate not limited to benzyl nitrite,
toluene dinitrite and aliphatic compounds and the like; in one
embodiment alkyl compounds, including but not limited to
substituted alkyl compounds and the like; in one embodiment purely
alkyl compounds; and in one embodiment, lower alkyl compounds;
combinations thereof. Examples of the nitrites as combustion
modifiers include but are not limited to methyl nitrite, propyl
dinitrite, hydroxymethyl propyl nitrite and,
1,3-dimorpholino-2-nitrite propane and combinations thereof. The
nitrites are combustion modifiers for the aqueous hydrocarbon fuel
and include but are not limited to 2,3-dimethyl-2,3 dinitrite
butane nitrite, pentaerythritol tetra nitrite, and nitrite
compounds of the formula: 4
[0066] Nitramines
[0067] At least one nitramine compound can be used as a combustion
modifier for the aqueous hydrocarbon fuel. The nitramine compounds
can be aliphatic or aromatic and may be mono- or
polynitramine-compounds. Polynitramine compounds are preferred.
Useful nitramine compounds include but are not limited to purely
hydrocarbon and substituted hydrocarbon nitramine compounds.
Examples of aromatic nitro compounds include benzyl nitramine,
phenyl nitramines, and aliphatic compounds, preferably alkyl
compounds, including substituted alkyl compounds, preferably purely
alkyl compounds and more preferably, lower alkyl compounds.
Examples include but are not limited to methyl nitramine 2-propyl
nitramine and more preferable the dinitramines, for example
ammonium dinitramine and ethylene dinitramine. And dinitramines for
example 5
[0068] molecules with two or more different functional groups.
[0069] At least one compound can be used as a combustion modifier
that has more than one functional group for the aqueous hydrocarbon
fuel. The disubstituted compounds can be aliphatic or aromatic and
may be mono- or polynitramine-compounds in combination with a
mono-or polynitro-compound. Useful disubstituted compounds include
purely hydrocarbon and substituted hydrocarbon nitramine compounds
with nitro or nitrate groups. Examples of disubstituted compounds
include but are not limited to 2-nitrophenol-3-nitramine, and
aliphatic compounds, preferably alkyl compounds, including
substituted alkyl compounds, preferably purely alkyl compounds and
more preferably, lower alkyl compounds. Examples include but are
not limited to 2,2-, nitro-nitramine propane More preferable would
be 2,4,6-trinitrophenylnitraaminoethyl nitrate.
[0070] The Hydrocarbon Fuel
[0071] The liquid hydrocarbon fuel comprises hydrocarbonaceous
petroleum distillate fuel, non-hydrocarbonaceous materials that
include but are not limited to water, oils, liquid fuels derived
from vegetables, liquid fuels derived from minerals and mixtures
thereof. Hydrocarbon based fuels are those fuels that contain
hydrocarbon groups, and especially those that are substantially
hydrocarbon, that is, those fuels derived from mineral oil sources
such as gasoline and middle distillate oils, for example, diesel
oil and heating oils, synthetic hydrocarbon fuels such as
polyolefins, alkylated aromatic hydrocarbon group containing fuels,
hydrocarbon fuels obtained by the Fischer-Tropsch process, and
others. Mixtures of hydrocarbon based fuels and oxygenates include
mixtures of any of the aforementioned hydrocarbon based fuels with
any of alkanols, especially lower alkanols, and ethers, for
example, methyl-t-butyl ether, methyl-t-amyl ether,
dimethoxymethane and diethoxymethane, and particularly, lower
alkanols such as ethanol. The liquid hydrocarbon fuel may be any
and all hydrocarbonaceous petroleum distillate fuels including not
limited to motor gasoline as defined by ASTM Specification D439 or
diesel fuel or fuel oil as defined by ASTM Specification D396 or
the like (kerosene, naphtha, aliphatics and paraffinics). The
liquid hydrocarbon fuels comprising non-hydrocarbonaceous materials
include but are 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; liquid fuels derived
from vegetable or mineral sources such as corn, alfalfa, shale,
coal and the like. The liquid hydrocarbon fuels also include
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.
In one embodiment, the liquid hydrocarbon fuel is any gasoline.
Generally, gasoline is a mixture of hydrocarbons having an ASTM
distillation range from about 60.degree. C. at the 10% distillation
point to about 205.degree. C. at the 90% distillation point. In one
embodiment, the gasoline is a chlorine-free or low-chlorine
gasoline characterized by a chlorine content of no more than about
10 ppm.
[0072] In one embodiment, the liquid hydrocarbon fuel is any diesel
fuel. Diesel 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. The diesel fuels
can be classified as any of Grade Nos. 1-D, 2-D or 4-D as specified
in ASTM D975. The diesel fuels may contain alcohols and esters. 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 D2622-87. In one embodiment, the diesel
fuel is a chlorine-free or low-chlorine diesel fuel characterized
by chlorine content of no more than about 10 ppm.
[0073] The liquid hydrocarbon fuel is present in the aqueous
hydrocarbon fuel emulsion 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 aqueous
hydrocarbon fuel emulsion.
[0074] The Water
[0075] The water used in the aqueous hydrocarbon fuel emulsion 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 antifreeze such as alcohols and
glycols, ammonium salts such as ammonium nitrate, ammonium maleate,
ammonium acetate and the like, and combinations thereof.
[0076] The water may be present in the aqueous hydrocarbon fuel
emulsions at a concentration of about 1% to about 50% by weight,
and in one embodiment about 5% to about 50% by weight, and in one
embodiment about 5% to about 40% being weight, and in one
embodiment about 5% to about 25% by weight, and in one embodiment
about 10% to about 20% water.
[0077] The Emulsifier
[0078] The emulsifier is any suitable emulsifier for emulsifying
the aqueous hydrocarbon fuel emulsion so that there is a
discontinuous aqueous phase having a mean diameter droplets of 1.0
micron or less in a continuous hydrocarbon fuel phase. Preferred
emulsifiers for the aqueous hydrocarbon fuel comprise:
[0079] (i) at least one fuel-soluble product made by reacting at
least one hydrocarbyl-substituted carboxylic acid acylating agent
with ammonia or an amine, the hydrocarbyl substituent of said
acylating agent having about 50 to about 500 carbon atoms;
[0080] (ii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0081] (iii) a mixture of (ii) with (i);
[0082] (iv) 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;
[0083] (v) 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, alkanol amine, or hydroxy
amines;
[0084] (vi) an amino alkylphenol which is made by reacting an
alkylphenol, an aldehyde and an amine resulting in an amino
alkylphenol, or
[0085] (vii) the combination of (vi) and (i), (ii), (iii), (iv),
(v) or combination thereof.
[0086] The emulsifier may be present in the aqueous hydrocarbon
fuel emulsion at a concentration of about 0.05% to about 20% by
weight, in another embodiment about 0.05% to about 10% by weight,
in another embodiment about 0.1% to about 5% by weight, and in a
further embodiment of about 0.01% to about 3% by weight of the
aqueous hydrocarbon fuel emulsion.
[0087] Fuel Soluble Product (i)
[0088] The fuel-soluble product (i) 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.
[0089] 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.
[0090] 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.
[0091] The fuel-soluble product (i) may be formed using ammonia, an
amine and/or 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.
[0092] 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.
[0093] The amines include but are not limited to
hydroxyalkylamines, 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; is a polyamine bottoms or a
heavy polyamine. The fuel-soluble product (i) may be a salt, an
ester, an ester/salt, an amide, an imide, or a combination of two
or more thereof.
[0094] The Ionic or Nonionic Compound (ii)
[0095] The ionic or nonionic compound (ii) 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. Useful compounds
include alkanolamides, 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. In the preferred
embodiment of an amine salt, it is a C.sub.8-C.sub.20 alkenyl
succinic ester amine salts such as the reaction product of an
alkenyl succinic anhydride with alkanol amine such as
N,N-dimethylethanol amine, N,N-diethylethanol amine or the
like.
[0096] Emulsifier Mixture (iii)
[0097] A mixture of (i) and (ii) is described in greater detail in
U.S. Ser. No. 09/761,482, An Emulsifier For An Aqueous Hydrocarbon
Fuel, incorporated by reference herein. The mixture of (i) and (ii)
is useful as an emulsifier for the aqueous hydrocarbon fuel.
[0098] The Water-Soluble Compound (iv)
[0099] The water-soluble compound may be an amine salt, ammonium
salt, azide compound, nitro compound, 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.
[0100] Particularly useful are the amine or ammonium salts such as
ammonium nitrate, ammonium acetate, methylammonium nitrate,
methylammonium acetate, ethylene diamine diacetate; urea nitrate;
urea; guanidinium nitrate; and combinations thereof.
[0101] Emulsifier (v)
[0102] In one embodiment the emulsifier (v) 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.
[0103] The fuel soluble product is made by reacting at least one
hydrocarbyl-substituted carboxylic agent with a hydroxy amine
and/or polyamine and is described earlier in the specification.
[0104] 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. The alpha-olefins include
1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,
1-eicosene, 1-docosene, 1-triacontene, and the like. the alpha
olefin fractions that are useful include C.sub.15-18 aipha-olefins,
C.sub.12-16 alpha-olefins, C.sub.14-16 alpha-olefins, C.sub.14-18
alpha-olefins, C.sub.16-18 alpha-olefins, C.sub.18-24
alpha-olefins, .sub.C18-30 alpha-olefins, and the like. Mixtures of
two or more of any of the foregoing alpha-olefins or alpha-olefin
fractions may be used.
[0105] Other polyacidic polymers suitable for reaction include but
are not limited to 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; and combinations thereof. The
preferred is polyacidic polymer C.sub.18 [1-octadecene]/maleic
anhydride copolymer.
[0106] In another embodiment the polyacidic polymer is a copolymer
of an olefin and a monomer having the structure: 6
[0107] 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.
[0108] The olefin includes a polymerizable olefin characterized by
the presence of one or more ethylenically unsaturated groups. The
olefin monomers include but are not limited to 1-hexene,
octadecene-1 and diisobutylene. The olefin preferably is a
C.sub.4-C.sub.30 olefin.
[0109] 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.
[0110] Amino Alkylphenol Emulsifier (vi) and (vii)
[0111] The amino alkyl emulsifier is comprised of the reaction
product of an alkylphenol, an aldehyde, and an amine resulting in
amino alkylphenol and is described in greater detail in U.S. Ser.
No. 09/977,742, A Continuous Process for Making an Aqueous
Hydrocarbon Emulsion, incorporated by reference herein. 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)
[0112] 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. For example, in place of the phenol,
alkyl-substituted compounds of resorcinol, hydroquinone, catechol,
cresol, xylenol, amyl phenol, hydroxydiphenyl, benzylphenol,
phenylethylphenol, methylhydroxydiphenyl, alpha and beta naphthol,
alpha and beta methylnaphthol, tolylinaphthol, xylylnaphthol,
benzylnaphthol, anthranol, phenylmethylnaphtol, phenanthrol,
monomethyl ether of catechol, phenoxyphenol, chlorophenol,
hydroxyphenyl sulfides and the like may be used.
[0113] 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.
[0114] 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.
[0115] The amines include, but are not limited to, alkanolamines
such as monoethanol amine, diethanolamine, N-(2-aminoethyl)
ethanolamine and the like; di- and polyamine (polyalkyene amines)
such as dimethylaminopropylamine, 3-aminopropyl morpholine,
ethylendiamine, diethylenetriamine, triethylene tetramine,
tetraethylene pentamine and the like including distillation bottoms
such as HPAX (commercially available from The Union Carbide
Corporation), E-100 (commercially available from Dow Chemical Co.),
and the like; polyalkyl polyamines; propylenediamine, the aromatic
amines such as o-, m- and p-phenylene diamine, diamino
naphthalenes; the acid-substituted polyalkylpolyamines, such as
N-acetyl tetraethylenepentamine, 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. (Secondary
heterocyclic amines that are suitable are those characterized by
attachment of a hydrogen atom to a nitrogen atom in the
heterocyclic group such as morpholine, thiomorpholine, pyrrole,
pyrroline, pyrrolidine, indole, pyrazole, pyrazoline, pyrazolidine,
imidazole, imidazoline, imidazolidine, piperidine, phenoxazine,
phenthiazine and their substituted analogs. Substituent groups
attached to the carbon atoms of these amines are typified by alkyl,
aryl, alkaryl, aralkyl, cycloalkyl, and amino compounds referred to
above.)
[0116] The "amine" includes, but is not to be limited, to the
product obtained by reacting an alkenyl succinic anhydride such as
succinic anhydride of the formula 7
[0117] or alkenyl succinic acid such as succinic acids of the
formula 8
[0118] with the amines of the foregoing paragraph.
[0119] In the above formulae, R is an alkylene group. The alkenyl
radical can be straight-chain or branched-chain; and it can be
saturated at the point of unsaturation by the addition of a
substance that adds to olefinic double bonds, such as hydrogen,
sulfur, bromine, chlorine, or iodine. There must be at least two
carbon atoms in the alkenyl radical, but there is no real upper
limit to the number of carbon atoms therein. The alkenyl succinic
acid anhydrides and the alkenyl succinic acids are interchangeable
for the purposes of the present invention. Nonlimiting examples of
the alkenyl succinic acid anhydride component are ethenyl succinic
acid anhydride; ethenyl succinic acid; ethyl succinic acid
anhydride; propenyl succinic acid anhydride; sulfurized propenyl
succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl
succinic acid anhydride; 1,2-dichloropentyl succinic acid
anhydride; hexenyl succinic acid anhydride; hexyl succinic acid;
sulfurized 3-methylpentyl succinic acid anhydride;
2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl
succinic acid; 1,2-dibromo-2-ethylbutyl succinic acid; heptenyl
succinic acid anhydride; 1,2-diiodooctyl succinic acid; octenyl
succinic acid anhydride; diisobutenyl succinic acid anhydride;
2-methylheptenyl succinic acid anhydride; 4-ethylhexenyl succinic
acid; 2-isopropylpentenyl succinic acid anhydride; nonenyl succinic
acid anhydride; 2-propylhexenyl succinic acid anhydride; decenyl
succinic acid; decenyl succinic acid anhydride;
5-methyl-2-isopropyl-hexenyl succinic acid anhydride;
1,2-dibromo-2-ethyloctenyl succinic acid anhydride; decyl succinic
acid anhydride; undecenyl succinic acid anhydride;
1,2-dichloroundecyl succinic acid; 3-ethyl-2-t-butylpentenyl
succinic acid anhydride; tetrapropenyl succinic acid anhydride;
tetrapropenyl succinic acid; triisobutenyl succinic acid anhydride,
2-propyl-nonyl succinic acid anhydride, 3-butyloctenyl succinic
acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl
succinic acid anhydride; hexadecenyl succinic acid anhydride;
sulfurized octadecenyl succinic acid; octadecyl succinic acid
anhydride; 1,2-dibromo-2-methylpen- tadecenyl succinic acid
anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl
succinic acid anhydride; 1,2-dichloro-2-methylnonade- cenyl
succinic acid anhydride; 2-octyldodecenyl succinic acid;
1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl
succinic acid; hexacosenyl succinic acid anhydride; hentriacontenyl
succinic acid anhydride and combinations thereof. In general,
alkenyl succinic acid anhydrides having from about 8 to about 35,
and preferably, from about 9 to about 18 carbon atoms in the
alkenyl group. Methods for preparing the alkenyl succinic acid
anhydrides are known to those familiar with the art, the most
feasible method comprising the reaction of an olefin with maleic
acid anhydride.
[0120] The reaction is prepared by any known method such as an
emulsion, a solution, a suspension, a continuous additive bulk
process or the like. The reaction is carried out under conditions
that provide for the formation of the desired product.
[0121] Additional Additives
[0122] In addition to the foregoing materials, other fuel additives
that are known to those of skill in the art may be used in the
aqueous hydrocarbon fuel emulsions of the invention. 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.
[0123] The water fuel compositions of the present invention may
contain other additives that are known to those skilled in the art.
These can include combustion modifiers, such as octane number
enhancers for gasoline, for example, anti-knock agents such as
tetra-alkyl lead compounds and certain ethers, cetane number
improvers for diesel fuels such as alkyl nitrates, lead scavengers
such as halo-alkanes, dyes, antioxidants such as hindered phenols,
lubricity agents, cold flow improvers, dispersants, surfactants,
rust inhibitors such as alkylated succinic acids and anhydrides and
derivatives thereof, bacteriostatic agents, auxiliary dispersants
and detergents, gum inhibitors, fluidizers, metal deactivators,
demulsifiers, anti-icing agents and the like. The fuel compositions
of this invention may be lead-containing or lead-free fuels.
Preferred are lead-free fuels.
[0124] The total concentration of additives, including the
emulsifiers, in the aqueous hydrocarbon fuel emulsions of the
invention may range 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.
[0125] Antifreeze Agent
[0126] The water-fuel emulsions of the invention 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 emulsions. 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 based on the weight of the water-fuel emulsion, and in one
embodiment about 0.1 to about 20% by weight, and in one embodiment
about 1 to about 10% by weight.
[0127] The Engines
[0128] The engines that may be operated in accordance with the
invention include all compression-ignition (internal combustion)
engines for both mobile (including locomotive and marine) and
stationary power plants. These include engines that use diesel,
gasoline, and the like. The engines that can be used include but
are not limited to those used in automobiles, trucks such as all
classes of truck, buses such as urban buses, locomotives, light and
heavy duty diesel engines, stationary engines and the like.
Included are on- and off-highway engines, including new engines as
well as in-use engines. These include diesel engines of the
two-stroke-per-cycle and four-stroke-per-cycle types.
Specific Embodiment
[0129] The following examples demonstrate the advantages of the
present invention.
EXAMPLE 1
[0130] A fuel composition (Purinox) contains 86% diesel fuel, 20%
water, 3% of an emulsifier packages containing 0.28%
N,N-diethylhydroxylamine hexadecyl substituted succinic ester-salt
prepared by reacting one mole each of hexadecyl substituted
succinic anhydride with dimethylethanolamine, 0.75% 2-ethylhexy
nitrate, 1.2% % N,N-diethylhydroxylamine hexadecyl substituted
succinic ester-salt prepared by reacting one mole each of 2000 MW
Polyisobutylene hexadecyl substituted succinic anhydride with
dimethylethanolamine, 0.5% ammonium nitrate, and 0.6% substituted
succinimide by reacting one mole each of 2000 MW Polyisobutylene
and hexadecyl substituted succinic anhydrides with
N,N-triiethyltetramine; to which emulsion is added 1 part
hydroxylamine nitrate (as sufficient 82% aqueous solution to
provide 0.85 parts, the remaining water contributing to the 18%
total water). This above fuel was tested in a Caterpillar 3176 at
South West Research Institute. The engine was operated at an 8 mode
steady state test simulating the Federal test procedure for
heavy-duty engines. The results on the emission test are shown
below.
[0131] The above example demonstrates the emission result on three
fuels as shown. The first fuel Purinox yielded a 19% reduction in
NOX as compared to base fuel. Purinox also yielded a 16% decrease
in Particulate Matter (PM) emissions. However, Purinox cause a 33%
increase in Hydrocarbons (HC) as well as a 41% increase in carbon
monoxide as compared to the base fuel. The second fuel labeled
Purinox+CM is the Purinox fuel plus a 1% solution of Hydroxy
Ammonium Nitrate (HAN) (82% concentrate in 18% water). This fuel
yielded a 13% reduction in NOX, a 30% reduction in PM, a 25%
decrease in HC and a 15 reduction in CO.
[0132] The third fuel had the same formulation as the second except
0.75% of 2-ethylhexyl nitrate was removed. It yielded a 14%
reduction in NOx, a 36.4% reduction in PM, a 7.2% reduction in HC
and a 1.1% reduction in CO.
[0133] From the above descriptions and examples of the invention,
those skilled in the art will perceive improvements, changes and
modifications in the invention. Such improvements, changes and
modifications within the skill in the art are intended to be
covered by the appended claims.
* * * * *