U.S. patent application number 10/554305 was filed with the patent office on 2007-05-31 for ethoxylated surfactants for water in oil emulsions.
Invention is credited to Stephen A. Di Biase, David Hobson, Alex Psaila.
Application Number | 20070119529 10/554305 |
Document ID | / |
Family ID | 33434957 |
Filed Date | 2007-05-31 |
United States Patent
Application |
20070119529 |
Kind Code |
A1 |
Hobson; David ; et
al. |
May 31, 2007 |
Ethoxylated surfactants for water in oil emulsions
Abstract
The invention relates to an emulsified water in oil composition
using a novel additive surfactant package containing a
PIBSA-derived surfactant with a molecular weight in the ranged
about 300 to 3000 and in the range of about 0.01% to about 10% by
weight of the composition and an alkylamine ethoxylated surfactant
in the range of about 0.01% to about 10% by weight of the
composition.
Inventors: |
Hobson; David; (Derbyshire,
GB) ; Psaila; Alex; (Surrey, GB) ; Di Biase;
Stephen A.; (Lakewood, OH) |
Correspondence
Address: |
The Lubrizol Corporation
Patent Administrator - Mail Drop 022B
29400 Lakeland Blvd
Wickliffe
OH
44092-2298
US
|
Family ID: |
33434957 |
Appl. No.: |
10/554305 |
Filed: |
April 20, 2004 |
PCT Filed: |
April 20, 2004 |
PCT NO: |
PCT/US04/12186 |
371 Date: |
January 25, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60466578 |
Apr 30, 2003 |
|
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|
Current U.S.
Class: |
149/1 |
Current CPC
Class: |
C10L 1/1824 20130101;
C10L 1/2225 20130101; C10L 1/1881 20130101; C10L 1/2383 20130101;
C10L 1/143 20130101; C10L 1/125 20130101; C10L 1/1985 20130101;
C10L 1/1802 20130101; C10L 1/328 20130101; C10L 1/238 20130101;
C10L 1/1266 20130101; C10L 1/2222 20130101; C10L 1/1826 20130101;
C10L 1/10 20130101; C10L 1/198 20130101; C10L 1/231 20130101 |
Class at
Publication: |
149/001 |
International
Class: |
C06B 47/00 20060101
C06B047/00 |
Claims
1. An emulsified water in oil composition: comprising: a) a fuel;
b) a water; c) an additive surfactants package comprising i) an
alkylamine ethoxylate wherein the alkylamine ethoxylate is selected
from the groups comprising tallow amine penta ethoxylate, tallow
amine tetra ethoxylate, tallow amine hexa ethoxylate, tallow amine
hepta ethoxylate, oleyl amine deca ethoxylate, oleyl amine undeca
ethoxylate, oleyl amine nona ethoxylate, oleyl amine dodeca
ethoxylate, tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane,
oleyl amine penta ethoxylate, oleyl amine diethoxylate, stearyl
alcohol penta ethoxylate, stearyl amine diethoxylate and
combinations thereof, and ii) a PIBSA-derived surfactant; and d)
optionally at least one of a functional amount of at least one
water-soluble, oil-insoluble functional additive dissolved in the
emulsified aqueous phase, and wherein a fuel is in the range of
about 50% to about 99% by weight of the composition; the water is
in the range of about 1% to about 50% by weight of the composition;
and the additive surfactant package is in the range of about 0.01%
to about 10% by weight of the composition, and wherein the additive
surfactant package is in the range of about 0.01% to about 10% by
weight of the water in oil composition.
2. The composition of claim 1 wherein the additive surfactant
package comprises: (a) at least one of an alkylamine ethoxylated
surfactant that is a mono- or a di-amine of the general formulae
and combinations thereof:
R--N(E.sub.aH)--(CH.sub.2).sub.x--N(E.sub.bH)(E.sub.cH) or
R--N(E.sub.aH)(E.sub.bH) wherein R=, straight or branched chained
alkyl group, C8 to C30, and saturated or unsaturated, containing
either 0, or 1, or 2 or 3 double bonds, wherein N=nitrogen atom,
wherein E is an ethoxylate group, --CH.sub.2--CH.sub.2--O--,
wherein x=1, 2, or 3, and wherein a, b, c,=an integer from 0 to 20
such that a+b+c=any value between 1 and 20; and (b) at least one of
a PIB based material comprising: (1) a PIBSA only; (2) a PIB
succinic acid; (3) a PIB succinic acid-amine salt; (4) a PIB
succinic aminoalkylester or ester-acid or amine salt thereof; (5) a
succinimide or succinamide or amide-acid salt thereof derived by
reacting PIBSA with an amine or poly amine; (6) a succinic ester
derived by reacting PIBSA with a polyol; or (7) combinations
thereof.
3. The composition of claim 2 wherein R is C10 to C24 and a+b+c=1
to 14 and wherein the water in oil composition is an emulsified
water blended fuel and wherein the fuel is selected from the group
comprising petroleum distillate fuel such as diesel, gasoline, fuel
oil a mixture thereof; a fuel derived from vegetables, corn,
alfalfa, rapeseed, soybeans, shale, coal or mixtures thereof; a
biodegradable fuel; biodiesel; residual fuel; bitumen; alcohol;
ether; ethanol; Fischer-Tropsch fuels: gas to liquids fuels and
combinations thereof.
4-6. (canceled)
7. The composition on claim 1 wherein the PIBSA-derived surfactant
has a PIB chain of molecular weight in the range of about 200 to
about 5000 and wherein the alkylamine ethoxylate is selected from
the groups comprising tallow amine penta ethoxylate, oleyl amine
deca ethoxylate,
tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane and
combinations thereof.
8-10. (canceled)
11. The composition of claim 2 wherein the additive surfactant
package is added to the following comprising: a) a hydrocarbon; b)
a water; c) optionally an antifreeze chemical; and d) optionally an
ammonium nitrate and wherein the PIB succinic acid-amine salt is
prepared by reacting the PIB succinic acid with either an alkyl
amine primary, secondary, or tertiary) or an ethanolamine and/or
ethoxylated amine and wherein the salt can be a fully neutralised
or partially neutralised salt, and wherein a PIB succinic
aminoalkylester or ester-acid or amine salt thereof is Prepared by
reacting the PIBSA or PIB succinic acid or ester thereof with a
hydroxylamine or an alkanol amine like ethanolamine and/or
ethoxylated amine and, wherein the salt can be a fully neutralised
or partially neutralized salt.
12. The composition of claim 1 wherein surfactants are used in
combination with the additive surfactant package but are not the
additive surfactant package surfactants and include but are not
limited to a) natural fats; b) ionics excluding the additive
surfactant package c) co-surfactants; d) fatty acids and their
amine salts; e) ethoxylate alcohols and f) combinations
thereof.
13. The composition of claim 2 wherein surfactants are used in
combination with the additive surfactant package but are not the
additive surfactant package surfactants and include but are not
limited to a) natural fats; b) ionics excluding the additive
surfactant package c) co-surfactants; d) fatty acids and their
amine salts; e) ethoxylate alcohols and f) combinations
thereof.
14-17. (canceled)
18. A process for making a water in oil emulsion comprising
emulsifying a fuel, a water, a PIBSA-derived surfactant and an
alkylamine ethoxylated surfactant to form an water in oil emulsion
and wherein the following components are added to the
emulsification in combination with the additive surfactant package
but are not the additive surfactant package surfactants and include
but are not limited to a) natural fats: b) ionics excluding the
additive surfactant package c) co-surfactants; d) fatty acids and
their amine salts: e) ethoxylate alcohols and f) combinations
thereof.
19. A process to produce an emulsified water in oil composition
from a concentrate comprising emulsifying a portion of a fuel, a
portion to substantially all of a water, substantially all of the
PIBSA-derived surfactant, substantially all of an alkylamine
ethoxylated surfactant to form a concentrate emulsion; and then
diluting the concentrated emulsion with the remaining portion of
fuel and water at the time of use.
20. The process of claim 18 wherein an antifreeze chemical and an
ammonium nitrate are added to the emulsification.
21. (canceled)
Description
RELATED APPLICATION
[0001] This is a continuation in part of U.S. Ser. No. 18/319668
filed on Dec. 13, 2002 entitled "An Emulsified Water Blended Fuels
Produced By Using A Low Energy Process And Novel Surfactant."
FIELD OF INVENTION
[0002] The invention relates to a novel additive package to produce
a water in oil emulsion, in particular water blended fuels with
good emulsion stability.
BACKGROUND OF THE INVENTION
[0003] Internal combustion engines, especially diesel engines,
using water fuel blends results in the combustion chamber producing
lower nitrogen oxides (NO.sub.x), hydrocarbons and particulate
matter emissions. NO.sub.x emissions have become an important
environmental issue because it contributes to smog and air
pollution. Governmental regulations and environmental concerns have
driven the need to reduce NO.sub.x emissions from engines. In
particular, the U.S. Clean Air Act will require about 90% to 95%
reduction of the current level of internal combustion engines
emissions by the year 2007. Similar regulations are expected in
Europe and other parts of the industrialized world.
[0004] Diesel fueled engines produce NO.sub.x due to the relatively
high flame temperatures reached during combustion. The reduction of
NO.sub.x production conventionally includes the use of catalytic
converters, using "clean" fuels, recirculation of exhaust and
engine timing changes. These methods are typically expensive or
complicated to be readily commercially available. Water is inert
toward combustion, but lowers the peak combustion temperature
resulting in reduced particulates and NO.sub.x formation. When
water is added to the fuel it forms an emulsion and these emulsions
are generally unstable. Stable water in fuel emulsions of a small
particle size are difficult to reach and maintain.
[0005] An emulsion fuel has to meet the specifications of diesel
fuel, as well as additional specifications which relate to an
emulsion fuel. For instance the Italian National specification
(Decreto 20 marzo 2000, published on 3 Apr. 2000 in Gazzetta
Ufficiale, n.78) imposes a stability test criterion, defined by a
centrifuge test (AFNOR prNFM 07-101). In the Italian specification
a sample of emulsion (defined as containing 12-15% water by weight)
is subjected to centrifugation (at a relative centrifugal force of
4200 for 5 minutes) and must show (i) no free water and, (ii) a
sedimented layer of compressed water emulsion not exceeding 9% by
volume. The standard also stipulates that no free water must be
formed for a further period of 4 months. The French National
specification defines similar criteria for emulsion stability.
[0006] Another important aspect of emulsion technology is the
energy required in order to make the emulsions. Various
technologies are available, for instance static mixers,
rotor-stator mills and ultrasonic devices. Whichever technology is
employed an important characteristic of a good emulsion system
(i.e. the two immiscible phases, the surfactants and carrier
fluids) is that it should emulsify quickly and, without undue high
expenditure of energy, form the desired emulsion giving a good
particle size distribution.
[0007] The use of emulsified fuels have been disclosed in other
patents and patent applications of Applicant, such as U.S. Pat.
Nos. 6,280,485, 6,383,237, 6,368,367, 6,368,366 and 6,280,485 and
U.S. Ser. No. 09/761,482 all incorporated herein by reference and
assigned to the assignee of the present application.
[0008] It would be advantageous to develop a stable water in fuel
emulsion. Further, it would be advantageous to make more stable
additive surfactant package for the use in water in oil
emulsions.
[0009] The present invention has discovered the use of surfactants
to make a water in oil emulsion/fuels. Further, the present
invention has discovered that a fatty amine ethoxylate and
derivatives of a PiB succinate surfactant is advantageous to
produce a water-in oil emulsion because (1) emulsification occurs
readily (low residence time in the mixer); (2) more stable
emulsions are formed; (3) in addition to the excellent colloidal
properties the resultant emulsified fuels show a markedly improved
performance in use with respects to elastomer compatibility and
corrosion; and (4) significant improvement in the overall stability
and ease of handling of the additive surfactant package.
[0010] The term "NO.sub.x" is used herein to refer to any of the
nitrogen oxides, NO, NO.sub.2, N.sub.2O, or mixtures of two or more
thereof. The terms "water-in-oil" emulsion, "water emulsion",
"emulsions", "water blended fuel", "emulsified water fuel" and
other variations are interchangeable.
SUMMARY OF THE INVENTION
The invention relates to an emulsified water in oil composition
comprising:
[0011] a. a fuel in the range of about 50% to about 99% by weight
of the composition;
[0012] b. a water in the range of about 1% to about 50% by weight
of the composition;
[0013] c. a polyisobutenyl succinic anhydride (PIBSA) derived
emulsifier wherein the molecular weight of the PIB chain is in the
range of about 200 to 5000 and in the range of about 0.01% to about
10%, or more preferred 0.02% to 5%, or more preferred 0.03% to
1.5%, by weight of the composition;
[0014] d. an alkylamine ethoxylated surfactant in the range of
about 0.01% to about 10%, or more preferred 0.02% to 5%, or more
preferred 0.03% to 1.5%, by weight of the composition; and
[0015] e. optionally at least one of a functional amount of at
least one water-soluble, oil-soluble functional additive dissolved
in the emulsified aqueous phase such as ammonium nitrate.
In particular the surfactant comprises:
[0016] (a) at least one of an alkylamine ethoxylated surfactant
that can be a mono- or a di- amine of the general formulae:
R--N(E.sub.aH)--(CH.sub.2).sub.x--N(E.sub.bH)(E.sub.cH) or
R--N(E.sub.aH) (E.sub.bH) wherein R equals straight or branched
chained alkyl group, C8 to C30, or more preferred C10 to C24, and
saturated or unsaturated, containing either 0, or 1, or 2 or 3
double bonds; N=nitrogen atom; E is an ethoxylate group,
--CH.sub.2--CH.sub.2--O-- x is either 1, 2, or 3, and a, b, c, is
an integer from 0 to 20 such that: a+b+c=any value between 1 and
20, more preferably between 1 and 14; and
[0017] (b) at least one PIBSA-derived material (with a PIB chain in
the molecular weight in the range of 200 to 5000) comprising:
[0018] (1) a PIBSA itself; [0019] (2) a PIB succinic acid, wherein
this material can be prepared by reacting a PIBSA with water;
[0020] (3) a PIB succinic acid-amine salt wherein this material can
be prepared by reacting the PIB succinic acid as described in (2)
with either an alkyl amine (primary, secondary, or tertiary) or an
ethanolamine and/or ethoxylated amine (A) described above and
wherein this salt can be a fully neutralised or partially
neutralised salt; [0021] (4) a PIB succinic aminoalkylester or
ester-acid or amine salt thereof. This material can be prepared by
reacting the PIBSA or PIB succinic acid as described in (1) and (2)
or ester thereof with a hydroxylamine or an alkanol amine like
ethanolamine and/or ethoxylated amine (A) described above, wherein
the salt can be a fully neutralised or partially neutralised salt;
[0022] (5) a succinimide or succinamide or amide-acid salt thereof
derived by reacting PIBSA with an amine or poly amine; [0023] (6) a
succinic ester derived by reacting PIBSA with a polyol; or [0024]
(7) combinations thereof.
[0025] Further, the invention relates to a process for making a
water in oil emulsion comprising emulsifying a fuel, a water, a
PIBSA-derived surfactant, and an alkylamine ethoxylated surfactant.
The invention further relates to a process to produce an emulsified
water in oil composition from a concentrate comprising emulsifying
a portion of a fuel, a portion to substantially all of a water,
substantially all of the PIBSA-derived surfactant, substantially
all of the alkylamine ethoxylated surfactant to form a concentrate
emulsion; and then diluting the concentrated emulsion with the
remaining portion of fuel at the time of use.
[0026] The water in oil emulsion provides good emulsion stability.
The additive package allows for the water in oil emulsion to be
processed more easily. Further the emulsion has increased storage
stability. The water in oil composition is useful as a fuel for
stationary and/or combustion engines and/or open flame burning
apparatus.
DETAILED DESCRIPTION
[0027] The invention discloses an additive surfactant package of at
least two surfactants to produce a stable emulsified water in oil
composition. The emulsified water in oil composition employs a
PIBSA derived surfactant and an alkylamine ethoxylated surfactant
which are identified by the term additive surfactant package
herein. The additive surfactant package has properties to lower the
interfacial tension at the water/oil interface during emulsion
formation.
[0028] The additive surfactant package is in the range of about
0.001% to about 15%, in another embodiment about 0.01% to about
10%, in another embodiment about 0.05% to about 5%, and in another
embodiment about 0.1% to about 3% by weight of the water in oil
composition. The additive surfactant package maybe used in
combination with other surfactants which may be either ionic or
non-ionic surfactant.
[0029] The alkylamine ethoxylated surfactant may be derived from a
mono-or a di-amine and has the general formulae:
R--N(E.sub.aH)--(CH.sub.2).sub.x--N(E.sub.bH)(E.sub.cH) or
R--N(E.sub.aH)(E.sub.bH) wherein R=, straight or branched chained
alkyl group, C8 to C30, preferably between C10 and C24, more
preferably C12 to C22 and most preferable C14 to C20 and saturated
or unsaturated, contained either 0, or 1, or 2 or 3 double bonds;
N=nitrogen atom; E is an ethoxylate group,
--CH.sub.2--CH.sub.2--O--; x=1, 2, or 3; and a, b, c,=any integer
between 0 and 20 such that: a+b+c=any value between 1 and 20, more
preferably between 1 and 14.
[0030] In another embodiment R is about C12 to about C22, and in
another embodiment about C10 to about C20.
[0031] The PIBSA-derived derived surfactant is selected from at
least one of or combinations of: [0032] (1) a PIBSA itself. [0033]
(2) a PIB succinic acid. This material can be prepared by reacting
a PIBSA with water. [0034] (3) A PIB succinic acid-amine salt. This
material can be prepared by reacting the PIB succinic acid as
described in (2) with either an alkyl amine (primary, secondary, or
tertiary), or an ethanolamine and/or ethoxylated amine (A)
described above. This salt can be a fully neutralised or partially
neutralised salt. [0035] (4) A PIB succinic aminoalkylester or
ester-acid or amine salt thereof. This material can be prepared by
reacting the PIBSA or PIB succinic acid as described in (1) and (2)
or ester thereof with a hydroxylamine or an alkanol amine like
ethanolamine and/or ethoxylated amine (A) described above, wherein
the salt can be a fully neutralised or partially neutralised salt.
[0036] (5) A succinimide or succinamide or amide-acid salt thereof
derived by reacting PIBSA with an amine or poly amine. [0037] (6) A
succinic ester derived by reacting PIBSA with a polyol.
[0038] The PIB based surfactant includes both non-ionic, ionic
materials or combinations thereof. The non-ionic materials include
PIB succinic acid and PIB succinamides The ionic materials include
PIB succinic acid salts. These are prepared by reaction of the
succinic acid with diethylethanolamine. Another embodiment of the
ionic material is an amidic acid salt.
[0039] The polyisobutylene chain of the PIBSA-derived surfactant
has a number average molecular weight of about 200 to about 5000,
in one embodiment about 1800 to about 2300, in one embodiment about
300 to about 3000, in one embodiment about 700 to about 1300, in
one embodiment about 800 to about 1000, and in one embodiment from
300 to 600. The PIBSA from which the PIBSA-derived surfactant is
prepared is characterized by about 1.3 to about 2.5, and in one
embodiment about 1.7 to about 2.1, succinic groups per equivalent
weight of the polyisobutylene substituent. 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.
[0040] Examples of alkylamines disclosed in (2) above include but
are not limited to 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 but are not limited to
trimethylamine, triethylamine, tripropylamine, tributylamine,
monoethyldimethylamine, dimethylpropylamine, dimethylbutyl-amine,
dimethylpentylamine, dimethylhexylamine, dimethylheptylamine, and
dimethyloctylamine.
[0041] The amines include but are not limited to hydroxyamines,
such as mono-, di-, and triethanolamine, dimethylethanol amine,
diethylethanol amine, di-(3-hydroxy propyl) amine,
N-(3-hydroxybutyl) amine, N-(4-hydroxy butyl) amine, and
N,N-di-(2-hydroxypropyl) amine; alkylene polyamines such as
methylene polyamines, ethylene polyamines, butylene polyamines,
propylene polyamines, pentylene polyamines, and the like. Specific
examples of such polyamines include but are not limited to ethylene
diamine, diethylene triamine, triethylene tetramine, propylene
diamine, trimethylene diamine, tripropylene tetramine,
tetraethylene pentamine, hexaethylene heptamine, pentaethylene
hexamine, or a mixture of two or more thereof; ethylene polyamine
bottoms or a heavy polyamine. In a preferred embodiment the
alkanolamine is diethyl ethanolamine.
[0042] The PIBSA-derived emulsifier may be present in the water
fuel emulsion at a concentration of 0.01% to about 10% by weight
based on the overall weight of the emulsion, and in one embodiment
about 0.02 to about 5% by weight, and an one embodiment about 0.03
to about 1.5% by weight.
[0043] Examples of suitable alkylamine ethoxylated surfactants
include but are not limited to tallow amine penta ethoxylate,
tallow amine tetra ethoxylate, tallow amine hexa ethoxylate, tallow
amine hepta ethoxylate, oleyl amine deca ethoxylate, oleyl amine
undeca ethoxylate, oleyl amine nona ethoxylate, oleyl amine dodeca
ethoxylate, tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane,
oleyl amine penta ethoxylate, oleyl amine diethoxylate, stearyl
alcohol penta ethoxylate and stearyl amine diethoxylate. In one
embodiment the alkylamine ethoxylated surfactant is tallow amine
penta ethoxylate. In one embodiment the alkylamine ethoxylated
surfactant is oleyl amine deca ethoxylate. In one embodiment the
alkylamine ethoxylated surfactant is
tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane. The
alkylamine ethoxylated surfactant can be used alone or in
combination.
[0044] The ethoxylated amine surfactant may be present in the water
fuel emulsion at a concentration of 0.01% to about 10% by weight
based on the overall weight of the emulsion, and in one embodiment
about 0.02 to about 5% by weight, and an one embodiment about 0.03
to about 1.5% by weight.
[0045] Further other surfactants may be used in combination with
the additive surfactant package but do not take the place of the
additive surfactant package and include but are not limited to a)
natural fats; b) ionics excluding the additive surfactant package
c) co-surfactants; d) fatty acids and their amine salts; e)
ethoxylate alcohols and f) combinations thereof.
[0046] The other non ionic and ionic surfactants include but are
not limited to alkyl ethoxylates, ethoxylated alkylphenols, alkyl
glucosides, ethoxylated alcohols, ethoxylated amines, amides
derived from fatty acids and/or alcohols, ethers or fatty alcohols,
esters of fatty acids and the like. In addition the non-ionic and
ionic surfactants have a hydrophilic lipohilic balance (HLB) in the
range of about 2 to about 40, in one embodiment, about 2 to about
10, in one embodiment about 10 to about 15 and in another
embodiment about 4 to about 8. Examples of these non-ionic and
ionic surfactants are disclosed in McCutcheon's Emulsifiers and
Detergents, 1993, North American & International Edition.
Preferably the non ionic surfactants are Neodol 25-3, C12-C 14
alcohol with two ethoxylates and Ethomeen C12. The non ionic and
ionic surfactants may be used alone or in combination.
[0047] The natural fat surfactants include but are not limited to
triglycerides, hydrolyzed triglycerides, oxidized products of
triglycerides, vegetable oils, refined vegetable oils, used
vegetable oils and the like. The preferred natural fat surfactant
is a refined used vegetable oil. The natural fats can be used alone
or in combination.
[0048] The co-surfactant has sufficient polar groups to render the
co-surfactant partially soluble in both phases. The co-surfactants
include but are not limited to alcohols, amines, amides, esters,
ketones, ethers and mixtures thereof. The co-surfactant has at
least 1 to about 24, in another embodiment about 1 to about 10, in
another embodiment about 1 to about 8 carbon atoms. The
co-surfactants may be used alone or in combination.
[0049] The fatty acids and their amine salts include but are not
limited to N,N-diethyl ethanolamine salts of oleic acid, tall oil
fatty acids, stearic acid, palmitic acid, lauric acid and the like.
The preferable fatty acid and their amine salt is oleic
acid-diethyl ethanol amine salt. The fatty acids and their amine
salts can be used alone or in combination.
Fuel
[0050] The fuel comprises hydrocarbonaceous petroleum distillate
fuel, non-hydrocarbonaceous materials that include but are not
limited to water, oils, liquid fuels derived from vegetable
sources, liquid fuels derived from minerals, liquid to gas, and
mixtures thereof. Suitable fuels include, but are not limited to,
gasoline, diesel, kerosene, naphtha, aliphatics and paraffin. The
fuel comprises non-hydrocarbonaceous materials include but is not
limited to alcohols such as methanol, ethanol and the like, ethers
such as diethyl ether, methyl ethyl ether and the like,
organo-nitro compounds and the like; fuels derived from vegetable
or mineral sources such as corn, alfalfa, shale, coal and the like.
The fuel also includes but is not limited to gas to liquid fuels,
Fischer-Tropsch fuels and the like. The fuel also includes but is
not limited to mixtures of one or more hydrocarbonaceous fuels and
one or more non-hydrocarbonaceous materials. Examples of such
mixtures are combinations of gasoline and ethanol and of diesel
fuel and ether and the like.
[0051] In one embodiment, the fuel is any gasoline. Including, but
not limited to a chlorine-free gasoline or a low-chlorine gasoline,
or a low sulfur gasoline or sulfur-free gasoline and the like.
[0052] In one embodiment, the fuel is any diesel fuel. The diesel
fuels include, but are not limited to, those that contain alcohols
and esters, has a sulfur content of up to about 0.05% by weight or
sulfur-free, is a chlorine-free or low-chlorine diesel fuel and the
like. In one embodiment the preferred fuel is a diesel fuel.
[0053] The fuel is present in the emulsified fuel at a
concentration of about 50% to about 95% by weight, and in one
embodiment about 60% to about 95% by weight, and in one embodiment
about 65% to about 85% by weight, and in one embodiment about 80%
to about 90% by weight of the emulsified fuel.
Water
[0054] The water used in the emulsified fuel may be taken from any
source. The water includes but is not limited to tap, deionized,
de-ionized to a conductivity of <30 microsiemens/cm and up to
50% v/v, demineralized, purified, for example, using reverse
osmosis or distillation, and the like. The water includes water
mixtures that further includes but are not limited to antifreeze
components such as alcohols and glycols, ammonium salts such as
ammonium nitrate, ammonium maleate, ammonium acetate and the like,
and combinations thereof; and other water soluble additives.
[0055] The water is present in the emulsified fuel at a
concentration of about 1% to about 50% by weight, in one embodiment
about 5% to about 40% being weight, in one embodiment about 5% to
about 25% by weight, and in one embodiment about 10% to about 20%
by weight of the emulsified fuel.
[0056] In another embodiment the water is present in the emulsified
fuel at a concentration of less than 1% by weight, in another
embodiment less than 0.5% by weight, in another embodiment less
than 0.1% by weight, and in another embodiment in the range of
about 0.1% to about 1% by weight of the emulsified fuel. An
emulsified water in oil composition can be made with water at these
low levels with the fuel, the emulsifier, the surfactant and
optionally ammonium nitrate and in another embodiment without the
surfactant and with the fuel, the emulsifier and optionally the
ammonium nitrate.
Other Additives
[0057] In one embodiment, the emulsified fuel contains a cetane
improver. The cetane improvers that are useful include but are not
limited to peroxides, nitrates, nitrites, nitrocarbamates and the
like. Useful cetane improvers include but are not limited to
nitropropane, dinitropropane, tetranitromethane,
2-nitro-2-methyl-1-butanol, 2-methyl-2-nitro-1-propanol, and the
like. Also included are nitrate esters of substituted or
unsubstituted aliphatic or cycloaliphatic alcohols which may be
monohydric or polyhydric. These include substituted and
unsubstituted alkyl or cycloalkyl nitrates having up to about 10
carbon atoms, and in one embodiment about 2 to about 10 carbon
atoms. The alkyl group may be either linear or branched, or a
mixture of linear or branched alkyl groups. Examples include but
are not limited to methyl nitrate, ethyl nitrate, n-propyl nitrate,
isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl
nitrate, sec-butyl nitrate, isooctyl nitrate, tert-butyl nitrate,
n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate,
tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, n-octyl
nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate,
n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate,
methylcyclohexyl nitrate, and isopropylcyclohexyl nitrate. Also
useful are the nitrate esters of alkoxy-substituted aliphatic
alcohols such as 2-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy) ethyl
nitrate, 1-methoxypropyl-2-nitrate, 4-ethoxybutyl nitrate, etc., as
well as diol nitrates such as 1,6-hexamethylene dinitrate. A useful
cetane improver is 2-ethylhexyl nitrate.
[0058] The concentration of the cetane improver in the emulsified
fuel is at any concentration sufficient to provide the emulsion
with the desired cetane number. In one embodiment, the
concentration of the cetane improver is at a level of up to about
10% by weight, and in one embodiment about 0.05% to about 10% by
weight, and in one embodiment about 0.05% to about 5% by weight,
and in one embodiment about 0.05% to about 1% by weight of the
emulsified fuel.
[0059] In addition to the foregoing materials, other fuel additives
that are known to those skilled in the art may be used in the
emulsified fuel. These include but are not limited to dyes, rust
inhibitors such as alkylated succinic acids and anhydrides,
bacteriostatic agents, gum inhibitors, metal deactivators, upper
cylinder lubricants and the like.
[0060] The additives, including the foregoing emulsifiers, may be
diluted with a substantially inert, normally liquid organic solvent
such as naphtha, benzene, toluene, xylene or diesel fuel to form an
additive concentrate which is then mixed with the fuel and water to
form the emulsified fuel.
[0061] The emulsified fuel may contain up to about 60% by weight
organic solvent, and in one embodiment about 0.01% to about 50% by
weight, and in one embodiment about 0.01% to about 20% by weight,
and in one embodiment about 0.1% to about 5% by weight, and in one
embodiment about 0.1% to about 3% by weight of the emulsified
fuel.
[0062] The emulsified fuel may additionally contain an antifreeze
agent. The antifreeze agent is typically an alcohol. Examples
include but are not limited to ethylene glycol, propylene glycol,
methanol, ethanol, glycerol and mixtures of two or more thereof.
The antifreeze agent is typically used at a concentration
sufficient to prevent freezing of the water used in the water fuel
emulsion. The concentration is therefore dependent upon the
temperature at which the fuel is stored or used. In one embodiment,
the concentration is at a level of up to about 20% by weight of the
emulsified fuel, and in one embodiment about 0.1% to about 20% by
weight, and in one embodiment about 1% to about 10% by weight of
the emulsified fuel.
[0063] The total concentration of the additives, in the emulsified
fuel is from about 0.05% to about 30% by weight, and in one
embodiment about 0.1% to about 20% by weight, and in one embodiment
about 0.1% to about 15% by weight, and in one embodiment about 0.1%
to about 10% by weight, and in one embodiment about 0.1% to about
5% by weight of the emulsified fuel.
Process
[0064] The water in oil emulsion is comprised of a continuous
fuel-phase, a discontinuous water or aqueous phase, an emulsifying
amount of an additive surfactant package and optionally other a
surfactants and optionally a functional additives such as ammonium
nitrate.
[0065] In the practice of the present invention the water in oil
emulsion is made by a batch, semi-batch or a continuous process. A
concentrate may be made and used. The process is capable of
monitoring and adjusting the flow rates of the fuel, additive,
surfactant, package, surfactants, other additives and/or water to
form a stable emulsion with the desired water droplet size. The
water phase of the emulsified fuel is comprised of droplets having
a mean diameter of about 1.0 microns or less, in another embodiment
about 0.8 microns or less, in another embodiment about 0.5 microns
or less, in another embodiment about 0.15 microns or more, in
another embodiment about 1.0 micron to about 0.5 microns, and in
another embodiment about 1.0 micron to about 0.2 microns.
[0066] The emulsified fuel may be prepared by the steps of mixing
the fuel, the emulsifier, the additive surfactant package, and
other oil soluble additive using shear techniques to form the fuel
additive mixture. Then the fuel additive mixture is mixed with
water and optionally any desired water soluble additives to form
the desired emulsified water blended fuel.
[0067] In a batch process the water, the additive surfactant
package, the fuel and optional additives are added to a tank, in
the desired amounts. The mixture is emulsified using an
emulsification device in the vessel, or alternatively the mixture
flows from the vessel via a circular line to the emulsification
device which is external to the vessel, for about 1 to about 20
tank turnovers. The temperature in the range of about ambient
temperature to about 100.degree. C. (212.degree. F.), and in
another embodiment in the range of about 4.degree. C. (40.degree.
F.) to about 65.degree. C. (150.degree. F.), and at a pressure in
the range of about atmospheric pressure to about 10 atmospheres, in
another embodiment about atmospheric pressure to about 80 psi, in
another embodiment in the range of about 1 to about 2 atm (15 psi
to about 30 psi).
[0068] The continuous process described herein depicts another
embodiment of the invention. The feeds of the fuel, additive
surfactant package, water and optional additives are introduced as
discrete feeds or in the alternative combinations of the discreet
feeds. The processing streams are introduced in or as close to the
inlet of the emulsification device as possible. It is preferable
that the emulsifier is added to the fuel as a fuel emulsifier
stream prior to the discreet feeds combining together. The
continuous process generally occurs under ambient conditions. The
continuous process is generally done at atmospheric pressure to
about 35 atm (500 psi), in another embodiment in the range of about
atmospheric pressure to about 8 to 9 atm (about 120 psi), and in
another embodiment in the range of about atmospheric pressure to
about 4 atm (about 50 psi). The continuous process generally occurs
at ambient temperature. In one embodiment the temperature is in the
range of about ambient temperature to about 100.degree. C.
(212.degree. F.), and in another embodiment in the range of about
4.degree. C. (40.degree. F.) to about 65.degree. C. (150.degree.
F.).
[0069] Alternatively, a concentrate is formed and all or
substantially all the water, and water soluble additive and a
portion of the fuel and all or substantially all the surfactant
packages is emulsified under shear conditions to form a concentrate
fuel. The emulsified fuel, when used, is then blended under normal
mixing conditions with the remaining portion remaining portion of
the fuel.
[0070] The process may be in the form of a containerized equipment
unit that operates automatically. The process can be programmed and
monitored locally at the site of its installation, or it can be
programmed and monitored from a location remote from the site of
its installation. The fully formulated water fuel blend is
optionally dispensed to end users at the installation site, or in
another embodiment end users can blend the concentrated emulsion
with the final portion of fuel. This provides a way to make the
water in fuel emulsions available to end users in wide distribution
networks.
[0071] The emulsification may occur at shear conditions are greater
than 50,000 s.sup.-1. However, the composition may be emulsified at
shear process conditions and occurs at a shear rate in the range of
less than or equal to 50,000 s.sup.-1, and in another embodiment
less the about 20,000 s.sup.-1, and in another embodiment less the
about 1,000 s.sup.-1, and in another embodiment less than 100 1
s.sup.-1, and in another embodiment less than 1 s.sup.-1. If more
than one emulsification step is used, the shear rates of the
emulsification steps can be the same, similar or different,
depending on the emulsifier and low molecular weight surfactant
used. The emulsification provides for the desired particle size and
a uniform dispersion of water in the fuel.
[0072] The emulsification occurs by any shear method used in the
industry including but not limited to mixing, mechanical mixer
agitation, static mixers, centrifugal pumps, positive displacement
pumps, orifice plates, and the like. Examples of the devices
include but are not limited to an Aquashear, pipeline static
mixers, rotor/stator mixers and the like. The Aquashear is a
low-pressure hydraulic shear device. The Aquashear mixers are
available from Flow Process Technologies Inc.
Engines
[0073] The engines that may be operated in accordance with the
invention include all (internal combustion) engines including spark
ignited (gasoline) and compression ignited (diesel) for both mobile
including locomotive, marine, automotive, truck, heavy duty,
aviation and the like, and stationary power plants. The engines may
be two-cycle or four-cycle. The engines may employ conventional
after treatment devices. Included are on- and off-highway engines,
including new engines as well as in-use engines.
[0074] An open-flame burning apparatus may be operated with the
emulsified water fuel blend of the invention. The open-flame
burning apparatus may be any open-flame burning apparatus equipped
to burn a liquid fuel. These include domestic, commercial and
industrial burners. The industrial burners include those requiring
preheating for proper handling and atomization of the fuel. Also
included are oil fired combustion units, oil fired power plants,
fired heaters and boilers, and boilers for use in ships including
deep draft vessels. The fuel burning apparatus may be a boiler for
commercial applications included are boilers for power plants,
utility plants, and large stationary and marine engines. The
open-flame fuel burning apparatus may be an incinerator or a rotary
kiln incinerator, liquid injection kiln, fluidized bed kiln, cement
kiln, and the like. Also included are steel and aluminium forging
furnaces. The open-flame burning apparatus may be equipped with a
flue gas recirculation system.
SPECIFIC EMBODIMENTS
Example 1
[0075] A fuel emulsion is prepared by mixing about 13 g of
de-ionised water, about 84.5 g of a commercially available diesel
containing less than 50 ppm of sulphur, about 0.523 g of 2300 MW
polyisobutylene succinic acid, about 0.06 g of diethyl
ethanolamine, about 0.562 g of tallow amine 7 mole ethoxylate,
about 0.305 g of 2-ethylhexylnitrate and about 1 g of diluent oil.
The mixture is sheared by mixing in an Ultra Turrax T25B
rotor-stator mixer for about 3 minutes.
Example 2
[0076] The emulsion is the same as Example 1 except the emulsion
additionally contains about 0.12 g of aqueous ammonium nitrate with
about 54% actives in solution.
Example 3
[0077] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.293
g of 2300 MW polyisobutylene succinic acid, about 0.0349 of diethyl
ethanolamine and about 0.943 g of tallow amine 7 mole ethoxylate
and about 0.04 g of ammonium nitrate is added and the emulsion is
sheared for about 30 seconds.
Example 4
[0078] The emulsion is the same as Example 3 except the emulsion is
sheared for about 2 minutes.
Example 5
[0079] The emulsion is the same as Example 3 except the emulsion is
sheared for about 5 minutes.
Example 6
[0080] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.375
g of 2300 MW polyisobutylene succinic acid, about 0.043 g of
diethyl ethanolamine and about 0.807 g of tallow amine 5 mole
ethoxylate and about 0.04 g of ammonium nitrate is added and the
emulsion is sheared for about 30 seconds.
Example 7
[0081] The emulsion is the same as Example 6 except the emulsion is
sheared for about 5 minutes.
Example 8
[0082] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.404
g of 2300 MW polyisobutylene succinimide derived by reacting PIBSA
with a polyamine and about 0.807 g of tallow amine 5 mole
ethoxylate and about 0.04 g of ammonium nitrate is added and the
emulsion is sheared for about 3 minutes.
Example 9
[0083] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.753
g of 1000 MW polyisobutylene succinimide derived by reacting PIBSA
with a polyamine and about 0.35 g of tallow amine 5 mole
ethoxylate.
Example 10
[0084] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.258
g of 1000 MW polyisobutylene succinic acid, about 0.142 g of 550 MW
polyisobutylene succinic acid, about 0.058 g of diethyl
ethanolamine, about 0.12 g of ammonium nitrate and about 0.561 g of
tallow amine 7 mole ethoxylate.
Example 11
[0085] The emulsion is the same as Example 1 except the amounts of
the following components in the emulsion are different, about 0.798
g of 2300 MW polyisobutylene succinic acid, about 0.024 g of
diethyl ethanolamine, about 0.12 g of ammonium nitrate, about 0.501
g of tallow amine 7 ethoxylate and about 0.056 g of oleyl amine 10
mole ethoxylate.
Test 1: Centrifuge Test
[0086] Approximately 40 g of emulsion is placed in calibrated,
graduated conical centrifuge tube and placed in a swing-out rotor
type centrifuge. The sample is centrifuged with a relative
centrifugal force of about 4200 for about 5 minutes (as stipulated
by the test method, AFNOR prNFM 07-101). The stability of the
emulsion is determined by measuring how much, if any, free water is
produced and the amount of sediment formed. The minimum
requirements are no free water and less than 9 volume % of the
emulsion is sedimented out. The results obtained were Table I:
TABLE-US-00001 TABLE I Example Sediment volume % 1 3.75 2 1.25 3
3.75 4 2.5 5 2.5 6 6.25 7 2.5 8 7.5 9 8.75 10 2.5 11 2.5
[0087] Examples 1-11 produce no free water after 5 minutes. Overall
Examples 1-11 pass the centrifuge test because they produce no free
water and the amount of sediment formed is below 9 volume %. The
test demonstrated that stable emulsions are produced.
Test 2: Particle Size
[0088] The particle size of an emulsion approximately 24 hours old
is determined by placing about 600 ml of diesel and about 0.5 ml of
emulsion in a Coulter LS230. The sample is exposed to a red laser
and the diffraction of micelles and measured on a detector. The
particle size distribution is then calculated. The results obtained
are shown in Table II.
[0089] A laser light scattering instrument is used to measure the
size distribution of water particles in PuriNOX.TM.. When light
encounters a particle, the particle scatters the light. The angular
dependence of this scattered light is dependent on the size of the
particle (relative to the wavelength of the incident light). By
measuring the intensity of the scattered light as a function of
angle, and by applying the Mie and Frauhofer scattering theory, the
particle size distribution can be determined. The Coulter LS230
uses an array of detectors to measure the intensity at 232 angles
simultaneously.
[0090] Particle size of the emulsion was determined by laser light
scattering technique (Coulter LS230 instrument) between 0.04 and
>50 micron metres. TABLE-US-00002 TABLE II Example % sub micron
1 92.5 2 100 3 91.4 4 98 5 95.3 6 70.4 7 96.9 8 61.5 9 72.2 10 13.3
11 100
[0091] Generally these measurements illustrate that excellent,
substantially sub-micron emulsions are obtained in all case, with
the exception of example 10. These data, in combination with the
centrifuge data, point to formulations which are close to optimal
and those (such as example 10) which are capable of improvement by
alteration of the surfactants (e.g. by either changing the
chemistry or changing the ratio of the surfactants).
Example 12
Formation of a Novel Ester/Acid Surfactants made by Reacting PIB
Succinic Anhydride (PIBSA) With Fatty Amine Ethoxylates
[0092] 1. Synthesis:
[0093] Composition A: a PIBSA, (2300 m.w. Glissopal succinic
anhydride), containing up to 30% solvent, was heated to about
80.degree. C. and held at this temperature while an equimolar
quantity of tallow amine 7 mole ethoxylate was added over about 15
to about 30 minutes. The reaction was followed by IR until the
anhydride peaks disappeared and the ester and carboxylic acid peaks
appeared, indicating that a reaction was complete.
[0094] Composition B: A second preparation was carried out
identical to Example A above except that the PIBSA was a 350 m.w.
PIBSA.
[0095] Glissopal was obtained from BASF and 350 m.w. PIB was
obtained from TCP.
[0096] 2. Evaluation
[0097] Example 12: A fuel emulsion is prepared by mixing about 13 g
of de-ionised water, about 84.48 g of a commercially available
diesel containing less than 50 ppm of sulphur, about 1.4269 of the
acid/ester illustrated in composition A above (i.e. made from 2300
MW polyisobutylene succinate and tallow amine 7 mole EO), about
0.305 g of 2-ethylhexylnitrate, about 0.12 g of aqueous (54%
concentrate) ammonium nitrate and about 0.67 g of diluent oil. The
mixture is sheared by mixing in an Ultra Turrax T25B rotor-stator
mixer for about 3 minutes.
Example 13
[0098] The emulsion is the same as Example 12 except the emulsion
was made with 1.426 g of the acid ester illustrated in Composition
B above (i.e. made from 350 MW polyisobutylene succinate and tallow
amine 7 mole EO).
Test 1: Centrifuge Test
[0099] Approximately 40 g of emulsion is placed in calibrated,
graduated conical centrifuge tube and placed in a swing-out rotor
type centrifuge. The sample is centrifuged with a relative
centrifugal force of about 4200 for about 5 minutes (as stipulated
by the test method, AFNOR prNFM 07-101). The stability of the
emulsion is determined by measuring how much, if any, free water is
produced and the amount of sediment formed. The minimum
requirements are no free water and less than 9 volume % of the
emulsion is sedimented out. The results obtained are shown in Table
III below. TABLE-US-00003 TABLE III Example Sediment volume % 12
6.25 13 2.5
[0100] Examples 12 and 13 produce no free water after 5 minutes.
Overall Examples 12 and 13 pass the centrifuge test because they
produce no free water and the amount of sediment formed is below 9
volume %. The test demonstrated that stable emulsions are
produced.
Test 2: Particle Size
[0101] The particle size of an emulsion approximately 24 hours old
is determined by placing about 600 ml of diesel and about 0.5 ml of
emulsion in a Coulter LS230. The sample is exposed to a red laser
and the diffraction of micelles and measured on a detector. The
particle size distribution is then calculated. The results obtained
are shown in Table IV below.
[0102] A laser light scattering instrument is used to measure the
size distribution of water particles in PuriNOX.TM.. When light
encounters a particle, the particle scatters the light. The angular
dependence of this scattered light is dependent on the size of the
particle (relative to the wavelength of the incident light). By
measuring the intensity of the scattered light as a function of
angle, and by applying the Mie and Frauhofer scattering theory, the
particle size distribution can be determined. The Coulter LS230
uses an array of detectors to measure the intensity at 232 angles
simultaneously.
[0103] Particle size of the emulsion was determined by laser light
scattering technique (Coulter LS230 instrument) between 0.04 and
>50 micron metres. TABLE-US-00004 TABLE IV Example % sub micron
12 81 13 100
[0104] Generally these measurements illustrate that excellent,
substantially sub-micron emulsions are obtained in both case. These
data, in combination with the centrifuge data, point to
formulations which are close to optimal.
[0105] From the above description and examples the invention those
skilled in the art may perceive improvements, changes and
modifications in the invention. Such improvement changes and
modifications are intended to be covered by the appended
claims.
* * * * *