U.S. patent application number 10/719158 was filed with the patent office on 2004-06-17 for continuous process for making an aqueous hydrocarbon fuel emulsion.
Invention is credited to Mullay, John J., Rowan, Stephen P., Westfall, David L..
Application Number | 20040111956 10/719158 |
Document ID | / |
Family ID | 34633235 |
Filed Date | 2004-06-17 |
United States Patent
Application |
20040111956 |
Kind Code |
A1 |
Westfall, David L. ; et
al. |
June 17, 2004 |
Continuous process for making an aqueous hydrocarbon fuel
emulsion
Abstract
An aqueous hydrocarbon fuel is produced by a batch or continuous
process. The process employs a reactant emulsion as a starting
component with a hydrocarbon fuel, emulsifier and water. The
resulting aqueous hydrocarbon fuel emulsion has improved
stability.
Inventors: |
Westfall, David L.;
(Lakewood, OH) ; Mullay, John J.; (Mentor, OH)
; Rowan, Stephen P.; (Mentor, OH) |
Correspondence
Address: |
Teresan W. Gilbert
The Lubrizol Corporation
Patent Dept. - Mail Drop 022B
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Family ID: |
34633235 |
Appl. No.: |
10/719158 |
Filed: |
November 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10719158 |
Nov 21, 2003 |
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09977747 |
Oct 15, 2001 |
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09977747 |
Oct 15, 2001 |
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09731173 |
Dec 6, 2000 |
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6530964 |
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09731173 |
Dec 6, 2000 |
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09483481 |
Jan 14, 2000 |
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6383237 |
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09483481 |
Jan 14, 2000 |
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09390925 |
Sep 7, 1999 |
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6368367 |
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09390925 |
Sep 7, 1999 |
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09349268 |
Jul 7, 1999 |
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6368366 |
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Current U.S.
Class: |
44/301 |
Current CPC
Class: |
C10L 1/328 20130101 |
Class at
Publication: |
044/301 |
International
Class: |
C10L 001/32 |
Claims
What is claimed:
1. A process to produce aqueous hydrocarbon fuel comprising
emulsifying components comprising: (A) a liquid hydrocarbon fuel;
(B) at least one emulsifier, wherein the emulsifier comprises: (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; (ii) at least one
of an ionic or a nonionic compound having a hydrophilic-lipophilic
balance (HLB) of about 1 to about 40; (iii) a mixture of (ii) with
(i); (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; (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, or hydroxy alkyl amines; (vi)
an amino alkylphenol which is made by reacting an alkylphenol, an
aldehyde and an amine, resulting in an amino alkylphenol; or (vii)
the combination of (vi) with (i), (ii), (iii), (iv), (v) or
combinations thereof; (C) a reactant emulsion comprising a water in
oil emulsion of a liquid hydrocarbon and at least one emulsifier
wherein the liquid hydrocarbon fuel and at least one emulsifier are
selected from the group of the same, similar, or different liquid
hydrocarbon fuel than the one used in step (A) and at least one
emulsifier disclosed in step B; and (D) a water mixture selected
from the group comprising water, water antifreeze, water ammonium
salt, water antifreeze ammonium nitrate mixture, and combinations
thereof, under emulsification conditions wherein the ratio of
hydrocarbon fuel, emulsifier and water to reactant emulsion is in
the range of about 1% to about 99% by weight hydrocarbon fuel,
emulsifier and water to about 99% to about 1% by weight reactant
emulsifier and wherein the emulsification shear rate results in an
emulsion having a particle size having a mean diameter of less than
1.0 micron.
2. The process of claim 1 wherein the resulting emulsion has a
particle size having a mean diameter in the range of about 1.0
micron to about 0.1 micron.
3. The process of claim 1 wherein about 50% to about 90% by weight
of the hydrocarbon fuel, about 0.1% to about 25% by weight of the
emulsifier, about 1% to about 90% by weight of the reactant
emulsion, and about 1% to about 90% by weight of the water, wherein
the water contains about 0% to about 10% by weight of water-soluble
additives are added to a vessel and wherein the ratio of
hydrocarbon fuel, emulsifier and water to reactant emulsion is
about 50% by weight hydrocarbon fuel, emulsifier and water to about
50% by weight reactant emulsion.
4. The process of claim 3 wherein the ratio of hydrocarbon fuel,
emulsifier and water to reactant emulsion is about 40% to about 60%
by weight hydrocarbon fuel, emulsifier and water to about 60% to
about 40% by weight reactant emulsion.
5. The process of claim 3 wherein the ratio of hydrocarbon fuel,
emulsifier and water to reactant emulsion is about 15% to about 85%
by weight hydrocarbon fuel, emulsifier and water to about 85% to
about 15% by weight reactant emulsion.
6. The process of claim 1 wherein the emulsifier is selected from
the group consisting of 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 (iii).
7. The process of claim 6 wherein the water-soluble compound is
ammonium nitrate.
8. The process of claim 1 wherein the components are emulsified in
a batch process for about 1 to about 20 tank turnovers at a
temperature in the range of about ambient temperature to about
212.degree. F. and at a pressure in the range of about atmospheric
to about 10 atmospheres, resulting in a stable aqueous hydrocarbon
fuel emulsion.
9. The process of claim 1 wherein the process is a continuous
process and wherein the feeds of hydrocarbon fuel, emulsifier,
reactant emulsion and the water are introduced as feeds selected
from the group consisting of discreet feeds and combinations of
discreet feeds and combinations thereof to form a homogeneous
aqueous hydrocarbon fuel emulsion and wherein the process occurs at
a temperature in the range of ambient temperature to about
212.degree. F. and at a pressure in the range of about atmospheric
pressure to about 500 psi.
10. The process of claim 1 wherein the emulsification occurs at a
shear rate in the range of greater than 0 s.sup.-1 to about 500,000
s.sup.-1 of shearing.
11. The process of claim 1 wherein the emulsification occurs at a
shear rate in the range of about 20,000 s.sup.-1 to about 200,000
s.sup.-1 shearing.
12. The process of claim 1 wherein the emulsification occurs at a
shear rate in the range of 25,000 s.sup.-1 to about 125,000
s.sup.-1 of shearing.
13. The process of claim 8 wherein at least one to five
emulsification steps in series is employed in the continuous
process.
14. The process of claim 9 wherein at least one to five
emulsification steps in series is employed in the continuous
process.
15. The process of claim 13 wherein there is no aging of the
hydrocarbon fuel water emulsion between each emulsification
step.
16. The process of claim 14 wherein the emulsion flows from one
emulsification step to the next emulsification step in less than 5
minutes.
17. The process of claim 14 wherein the emulsion flows from one
emulsification step to the next emulsification step in less than 3
minutes.
18. The process of claim 14 wherein the emulsion flows from one
emulsification step to the next emulsification step in less than 1
minute.
19. The process of claim 14 wherein the emulsion flows from one
emulsification step to the next emulsification step in less than 30
seconds 20. The process of claim 9 wherein the reactant emulsion is
formed from recycling the emulsion hydrocarbon fuel emulsion made
in a continuous process.
21. The process of claim 8 wherein the reactant emulsion is formed
from recycling the emulsion hydrocarbon fuel made in a batch
process.
22. The process of claim 1 wherein the reactant emulsion comprises
about 50% to about 99% by weight hydrocarbon fuel and about 0.05%
to about 25% by weight of at least one emulsifier.
23. The process of claim 1 wherein the reactant emulsion is
selected from the group that is the same, similar or different
emulsion then the aqueous hydrocarbon fuel.
Description
[0001] This is a continuation in part of U.S. application Ser. No.
09/977,747 filed Oct. 15, 2001, and is a continuation in part of
U.S. application Ser. No. 09/731,173 filed Dec. 6, 2000, which is a
continuation in part of Ser. No. 09/483,481 filed Jan. 14, 2000,
which is a continuation in part of U.S. application Ser. No.
09/390,925 filed Sep. 7, 1999, which is a continuation in part of
U.S. application Ser. No. 09/349,268 filed Jul. 7, 1999, and which
is a continuation in part of Ser. No. 09/761,482 filed Jan. 16,
2001, which is a continuation of Ser. No. 09/755,577 filed Jan. 5,
2001. All of the disclosures in the prior applications are
incorporated herein by reference in their entirety.
TECHNICAL FIELD
[0002] The invention relates to a process for making aqueous
hydrocarbon fuel emulsions from a continuous or batch process with
good stability. More particularly, the invention relates to a
process for making an aqueous hydrocarbon fuel emulsion by
employing an initial emulsion as one of the reactants in the
process.
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 (NOx), hydrocarbons and particulate
emissions per unit of power output. The reduction of nitrogen
oxides is an environmental issue because they contribute to smog
and air pollution. Governmental regulations and environmental
concerns have driven the need to reduce NOx emissions from
engines.
[0004] Diesel-fueled engines produce NOx due to the relatively high
flame temperatures reached during combustion. The reduction of NOx
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.
[0005] Water is inert toward combustion, but lowers the peak
combustion temperature resulting in reduced particulates and NOx
formation. When water is added to the fuel it forms an emulsion and
these emulsions are generally unstable. Stable water in fuel
emulsions of small particle size is difficult to reach and
maintain.
[0006] Stable water in fuel macroemulsions of small particles size
are difficult to make. It would be advantageous to develop a
process to make water in fuel macroemulsions in which a batch
process did not need a statistical number of tank turnovers to
produce a 1.0 micron or less water in fuel emulsion. Further, it
would be advantageous to produce submicron mean average particles
in a water in fuel macroemulsion by a continuous process.
[0007] It has been found that including an emulsion as an initial
component with the water fuel and emulsifier in a batch or
continuous process produces an improved stable water in fuel
macroemulsion with a mean average particle size distribution of 1
micron or less.
[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" are interchangeable. The terms "aqueous hydrocarbon
fuel" and "water fuel blend" are interchangeable.
SUMMARY OF THE INVENTION
[0009] The invention relates to a batch or continuous process for
making an aqueous hydrocarbon fuel emulsion comprising: emulsifying
(a) a liquid hydrocarbon fuel, water and at least one emulsifier,
(b) a reactant emulsion of the liquid hydrocarbon fuel, water and
at least one emulsifier, and (c) water, under emulsification
conditions to form an aqueous hydrocarbon fuel emulsion.
[0010] The aqueous hydrocarbon fuel is an emulsion comprised of
water, fuel and an emulsifier. The emulsifier comprises:
[0011] (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;
[0012] (ii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0013] (iii) a mixture of (ii) with (i);
[0014] (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;
[0015] (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;
[0016] (vi) an amino alkylphenol which is made by reacting an
alkylphenol, an aldehyde and an amine resulting in an amino
alkylphenol, or
[0017] (vii) the combination of (vi) with (i), (ii), (iii), (iv),
(v) or combinations thereof.
[0018] The aqueous hydrocarbon fuel emulsion includes a
discontinuous aqueous phase in a continuous fuel phase. The
discontinuous aqueous phase comprises aqueous droplets having a
mean diameter of 1.0 micron or less. Furthermore, the use of an
emulsion as an initial component in the batch or continuous process
has improved the efficiency of the process and the stability of
aqueous hydrocarbon emulsions for use as aqueous hydrocarbon fuel
emulsion.
[0019] The Process
[0020] The invention provides for a batch or continuous process for
making an aqueous hydrocarbon fuel by forming a stable emulsion in
which the water is suspended in a continuous phase of fuel and
wherein the water droplets have a mean diameter of 1.0 micron or
less. The droplet size is in volume.
[0021] In the practice of the present invention the aqueous
hydrocarbon fuel emulsion is made by a batch or a continuous
process capable of monitoring and adjusting the flow rates of the
reactant emulsion, fuel, emulsifier, additives and/or water to form
a stable emulsion with the desired water droplet size.
[0022] The batch process as described herein depicts one embodiment
of the invention. The hydrocarbon fuel, emulsifier, and reactant
emulsion are added to a vessel. The water is added to the vessel
or, in the alternative is added close to the entry portal of the
emulsification device, which is external to the vessel. In the
batch process the following components are emulsified:
[0023] (1) about 10% to about 90% by weight of the fuel and about
at least 0.1% to about 25% by weight of emulsifier,
[0024] (2) about 1% to about 90% by weight of a reactant emulsion,
and
[0025] (3) about 1% to about 50% by weight of water, wherein the
water contains about 0% to about 30% by weight of the aqueous
hydrocarbon emulsion.
[0026] The ratio of fuel, water and emulsifier to reactant emulsion
is about 1 to about 99, in another embodiment about 15 to about 85,
in another embodiment about 40 to about 60, in another embodiment
about 99 to about 1, in another embodiment about 85 to about 15, in
another embodiment about 60 to about 40, and in another embodiment
50 to about 50.
[0027] 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, at a
temperature in the range of about ambient temperature to about
212.degree. F., and in another embodiment in the range of about
40.degree. F. to about 150.degree. F., and at a pressure in the
range of about atmospheric pressure to about 10 atmospheres, in
another embodiment about atmosphere pressure to about 60 psi, in
another embodiment in the range of about 10 psi to about 40 psi,
resulting in stable aqueous hydrocarbon fuel emulsion with a mean
droplet size of less than 1.0 micron, and in another embodiment in
the range of about 1.0 micron to about 0.1 micron.
EXAMPLES 1-4
[0028] These examples are illustrations of making the hydrocarbon
fuel emulsion product by a batch process. The blending equipment
consists of a five-million-gallon-per-year batch blender.
[0029] Batch No. 1, using a 3:1 volume/volume ratio of raw material
components to reactant emulsion:
[0030] 1. A 25 gallon batch of hydrocarbon fuel emulsion was
prepared using about 19.9 gallons of diesel fuel, about 4.4 gallons
of water, and about 0.7 gallons of emulsifier A, which is the
following:
1 Concentrate % by weight Emulsifier 1 40.00 Emulsifier 2 7.14
Emulsifier 3 19.80 2-ethylhexylnitrate 23.80 Ammonium Nitrate 9.26
(54% by weight in water) Emulsifier 1: Reaction product of
dimethylethanolamine and PIBSA (Mn-2000) Emulsifier 2: Reaction
product of dimethylethanolamine and hexadeclysuccinnic anhydride
Emulsifier 3: Reaction product of an ethylene polyamine and PIBSA
(Mn-1000)
[0031] This 25 gallons was left in the processing tank to serve as
the reactant emulsion for the next batch.
[0032] 2. About 59.6 gallons of diesel fuel was added to the
processing tank followed by about 2.1 gallons of emulsifier A.
[0033] 3. The reactant emulsion, diesel fuel, and emulsifier A were
circulated through an IKA high shear mixer for about 30 seconds and
back to the processing tank.
[0034] 4. Following about 30 second mix and while continuing to
circulate through the mixer, a total of about 13.3 gallons of water
were added through a charging line immediately upstream of the
mixer. The water feed time was about 85 seconds.
[0035] 5. Once all water was added, the mixture continued to
circulate through the IKA mixer for about an additional 12 minutes
and 36 seconds.
[0036] 6. Samples of emulsion were taken from the processing tank
at various time intervals during this mix period representing 1, 2,
4, 7 and 9 tank turnovers. A tank turnover is defined as the
duration to pump 100 gallons through the mixer.
[0037] 7. The results are found in Table I.
[0038] Batch No. 2, using a 1:1 volume/volume ratio of raw material
components to reactant emulsion.
[0039] 1. A 50.1 gallon batch of hydrocarbon fuel emulsion was
prepared using about 39.8 gallons of diesel fuel, about 8.9 gallons
of water, and about 1.4 gallons of emulsifier A. This 50.1 gallons
were left in the processing tank to serve as the reactant emulsion
for the next batch.
[0040] 2. About 39.7 gallons of diesel fuel was added to the
processing tank followed by about 1.4 gallons of emulsifier A.
[0041] 3. The reactant emulsion, diesel fuel and emulsifier A were
circulated through the IKA high-shear mixer for about 30 seconds
and back to the processing tank.
[0042] 4. Following about 30 second mix and while continuing to
circulate through the mixer, a total of about 8.8 gallons of water
was added through a charging line immediately upstream of the
mixer. The water feed time was about 56 seconds.
[0043] 5. Once all water was added, the mixture continued to
circulate through the IKA mixer for about an additional 12 minutes
and 36 seconds.
[0044] 6. Samples of emulsion were taken from the processing tank
at various time intervals during this mix period representing 1, 2,
4, 7 and 9 tank turnovers. A tank turnover is defined as the
duration to pump 100 gallons through the mixer.
[0045] 7. The results are found in Table I.
[0046] Batch No. 3, using a 3:1 volume/volume ratio of raw material
components to reactant emulsion. A concentrated emulsion formula
was used for this example whereby approximately 85% volume of the
formula amount of diesel fuel was omitted during the
processing.
[0047] 1. A 25.1 gallon batch of concentrated aqueous hydrocarbon
fuel emulsion was prepared using about 8.6 gallons of CARB diesel
fuel, about 14.2 gallons of water and about 2.3 gallons of
emulsifier A. About 25.1 gallons were left in the processing tank
to serve as the reactant emulsion for the next batch.
[0048] 2. About 25.6 gallons of CARB diesel fuel were added to the
processing tank followed by about 6.6 gallons of emulsifier A.
[0049] 3. The reactant emulsion, diesel fuel and emulsifier A were
circulated through the IKA high shear mixer for about 30 seconds
and back to the processing tank.
[0050] 4. Following about 30 second mix and while continuing to
circulate through the mixer, a total of about 42.7 gallons of water
was added through a charging line immediately upstream of the
mixer.
[0051] 5. Once all water was added, the mixture continued to
circulate through the IKA mixer for about an additional 16
minutes.
[0052] 6. Samples of concentrated emulsion were taken from the
processing tank at various time intervals during this mix period
representing 1, 2, 4, 7 and 10.4 tank turnovers. A tank turnover is
defined as the duration to pump 100 gallons through the mixer.
[0053] 7. The concentrated emulsion was pumped to the diluter tank
and diluted with about 229.3 gallons of CARB diesel fuel.
[0054] 8. The diluter tank was circulated with a centrifugal pump
for about 9 minutes.
[0055] 9. A sample of the aqueous hydrocarbon fuel emulsion was
taken from the processing tank.
[0056] 10. The results are found in Table I.
[0057] Batch No. 4, using a 1:1 volume/volume ratio of raw material
components to reactant emulsion. A concentrated emulsion formula
was used for this example whereby approximately 85% volume of the
formula amount of diesel fuel was omitted during processing.
[0058] 1. About 50.1 gallon batch of concentrated aqueous
hydrocarbon fuel emulsion was prepared using about 17.1 gallons of
CARB diesel fuel, about 28.5 gallons of water, and about 4.5
gallons of emulsifier A. About 50.1 gallons were left in the
processing tank to serve as the reactant emulsion for the next
batch.
[0059] 2. About 17.1 gallons of CARB diesel fuel were added to the
processing tank followed by about 4.4 gallons of emulsifier A.
[0060] 3. The reactant emulsion, diesel fuel, and emulsifier A were
circulated through the IKA high shear mixer for about 30 seconds
and back to the processing tank.
[0061] 4. Following about 30 second mix and while continuing to
circulate through the mixer, a total of about 28.4 gallons of water
were added through a charging line immediately upstream of the
mixer.
[0062] 5. Once all water was added, the mixture continued to
circulate through the IKA mixer for about an additional 16
minutes.
[0063] 6. Samples of concentrated emulsion were taken from the
processing tank at various time intervals during this mix period
representing 1, 2, 4, 7 and 10.4 tank turnovers. A tank turnover is
defined as the duration to pump 100 gallons through the mixer.
[0064] 7. The concentrated emulsion was pumped to a diluter tank
and diluted with about 229.3 gallons of CARB diesel fuel.
[0065] 8. The diluter tank was circulated with a centrifugal pump
for about 9 minutes.
[0066] 9. A sample of the final aqueous hydrocarbon fuel emulsion
was taken from the diluter tank.
[0067] 10. The results are found in Table I.
2 TABLE I Particle Size Distribution 7 day static storage 7 day
static storage Mean Mode (room temperature) (43.degree. C.) Sample
description .mu.m .mu.m % Oily % White % Band % Oil % Oily % White
% Band Example 1: 1:24 mn:sec 0.78 0.47 6 94 3 9 91 7 Example 1:
2:48 mn:sec 0.77 0.47 6 94 4 9 91 7 Example 1: 5:36 mn:sec 0.77
0.52 4 96 4 9 91 7 Example 1: 9:48 mn:sec 0.79 0.52 4 96 4 9 91 7
Example 1: 12:36 mn:sec 0.78 0.52 6 94 4 9 91 7 Example 2: 1:24
mn:sec 0.63 0.43 6 94 4 6 94 6 Example 2: 2:48 mn:sec 0.64 0.43 6
94 4 7 93 6 Example 2: 5:36 mn:sec 0.68 0.47 4 96 4 7 93 6 Example
2: 9:48 mn:sec 0.63 0.47 6 94 3 7 93 6 Example 2: 12:36 mn:sec 0.63
0.47 4 96 3 7 93 6 Example 3: 1:32 mn:sec 1.31 1.45 Example 3: 3:04
mn:sec 1.40 1.59 Example 3: 6:06 mn:sec 1.30 0.91 Example 3: 10:44
mn:sec 1.05 1.20 Example 3: 16:00 mn:sec 0.92 1.24 Example 3: final
sample 0.89 0.63 3 97 7 3 6 91 12 Example 4: 1:32 mn:sec 1.12 1.32
Example 4: 3:04 mn:sec 1.05 1.00 Example 4: 6:06 mn:sec 0.98 1.00
Example 4: 10:44 mn:sec 0.90 0.83 Example 4: 16:00 mn:sec 0.83 0.76
Example 4: final sample 0.86 0.83 3 97 7 4 4 91 10
[0068] The continuous process described herein depicts another
embodiment of the invention. The feeds of the hydrocarbon fuel,
emulsifier, reactant emulsion and water are introduced as discreet
feeds or in the alternative combinations of the discreet feeds, to
form a homogeneous hydrocarbon fuel emulsion. It is preferable that
the processing streams of the fuel, emulsifier, water and emulsion
reactant, are introduced as close to the inlet of the
emulsification device as possible. It is preferable that the
emulsifier is added to the fuel as a hydrocarbon fuel emulsifier
stream prior to the discreet feeds combining together.
[0069] The ratio of the hydrocarbon fuel, emulsifier and water to
reactant emulsion in one embodiment is about 1% hydrocarbon fuel,
emulsifier and water to about 99% reactant emulsion, in another
embodiment about 99% hydrocarbon fuel, emulsifier and water to
about 1% reactant emulsion, in another embodiment about 15%
hydrocarbon fuel, emulsifier and water to about 85% reactant
emulsion, in another embodiment about 40% hydrocarbon fuel,
emulsifier and water to about 60% reactant emulsion, in another
embodiment about 60% hydrocarbon fuel, emulsifier and water to
about 40% reactant emulsion, and in another embodiment 50%
hydrocarbon fuel, emulsifier and water to about 50% reactant
emulsion. The hydrocarbon fuel emulsifier stream during startup and
shutdown is such that the ratio of water to hydrocarbon fuel
emulsion mixture is never greater than the steady state
condition.
[0070] The continuous process generally occurs under ambient
conditions. The continuous process is generally done at atmospheric
pressure to about 500 psi, in another embodiment in the range of
about atmospheric pressure to about 120 psi, and in another
embodiment in the range of about atmospheric pressure to about 50
psi. The continuous process generally occurs at ambient
temperature. In one embodiment the temperature is in the range of
about ambient temperature to about 212.degree. F., and in another
embodiment in the range of about 40.degree. F. to about 150.degree.
F.
[0071] The emulsification provides for the desired particle size
and a uniform dispersion of water in the fuel and occurs at a shear
rate in an embodiment greater than 0 s.sup.-1 to about 500,000,000
s.sup.-1, in another embodiment greater than 0 s.sup.-1 to about
100,000,000 s.sup.-1, in one embodiment about 500,000 s.sup.-1 to
about 500,000,000 s.sup.-1, in another embodiment about 100,000
s.sup.-1 to about 10,000,000 s.sup.-1, in another embodiment
greater than 0 s.sup.-1 to about 500,000 s.sup.-1, in another
embodiment about 75,000 s.sup.-1 to about 1,000,000 s.sup.-1, in
another embodiment about 20,000 s.sup.1 to about 200,000 s.sup.-1,
and in another embodiment of about 25,000 s.sup.-to about 125,000
s.sup.-1 of shearing. If more than one emulsification step is used,
the shear rates of the emulsification steps can be the same,
similar or different, depending on the emulsifier used and the
ratio of reactant emulsion to fuel additive and/or water.
[0072] In another embodiment the emulsion flows through at least
one to several emulsification devices. In another embodiment, the
emulsion flows through the next one to five emulsification devices.
The emulsion flows through the emulsion devices in series, directly
from one emulsification device to the next emulsification device in
the series.
[0073] In one embodiment there is no intermediate holding tank
between the emulsification steps. The emulsion is not aged between
the emulsification steps. Generally the time the emulsion flows
from one emulsification device to another emulsification device in
less than 5 minutes, in another embodiment less than 4 minutes, in
another embodiment less than 3 minutes, in another embodiment less
than 2 minutes, in another embodiment less than 1 minute, and in
another embodiment less than 30 seconds.
[0074] The other emulsification steps, in series, are a high-shear
process and occur under ambient conditions as described in the
emulsification step above. The shear rate temperature and pressure
can be the same, similar or different than the other emulsification
steps so long as the conditions are such to provide the desired
mean droplet particle size.
[0075] The emulsification step is a high shear process and results
in a uniform dispersion of the hydrocarbon fuel emulsion having a
mean particle droplet size in the range of about 0.1 micron to
about 1 micron, in one embodiment in the range of about 0.1 micron
to about 0.95 micron, in one embodiment in the range of about 0.1
micron to about 0.8 micron, and in one embodiment in the range of
about 0.1 micron to about 0.7 micron, and in one embodiment in the
range of about 0.2 micron to about 0.5 micron. A critical feature
of the invention is that the water phase of the aqueous fuel
emulsion product is comprised of water droplets having a mean
diameter of less than one micron, in another embodiment one micron
to about 0.1 micron, and in another embodiment 1.0 micron to about
0.2 micron.
[0076] The emulsification occurs by any method known in the
industry including but not limited to mixing, mechanical mixer
agitation, static mixers, shear mixers, sonic mixers, high-pressure
homogenizers, and the like. Examples of the emulsification devices
include but are not limited to an Aquashear, pipeline static mixers
and the like. The Aquashear is a low-pressure hydraulic shear
device. The material is forced through two facing plates with
drilled holes into the mixing chamber. The two plates cause counter
rotational flow and allow the material to mix. The Aquashear mixers
are available from Flow Process Technologies Inc.
[0077] Additional emulsification devices include high-shear devices
such as IKA Works, Inc. Dispax Reactor. The IKA shear mixers use a
DR3-6 with three stages of rotor/stator combinations. The tip speed
of the rotor/stator generators may be varied by a variable
frequency drive that controls the motor. The Silverson mixer is a
two-stage mixer, which incorporates a rotor/stator design. The
mixer has high-volume pumping characteristics similar to
centrifugal pump. Inline shear mixers by Silverson Corporation (a
rotor-stator emulsification approach); Jet Mixers
(venturi-style/cavitation shear mixers), cavitation technology,
cavitation devices, hydrodynamic cavitation, cavitation bubble
dynamics, controlled flow cavitation and the like, Ultrasonolator
made by the Sonic Corp. (ultrasonic emulsification approach),
Microfluidizer shear mixers available by Microfluidics Inc.
(high-pressure homogenization shear mixers), ultrasonic mixers, and
any other available high-shear mixer.
[0078] These emulsification devices have to have the ability to
reduce the mean particles size of the water droplet in the range of
less than one micron to about 0.1 micron or even less.
[0079] The hydrocarbon fuel, at least one emulsifier and water are
emulsified to form a reactant emulsion. The reactant emulsion is
formed from recycling the aqueous hydrocarbon fuel emulsion or
separately by emulsifying the hydrocarbon fuel with at least one
emulsifier in a separate vessel. The water may optionally contain
water-soluble additives. The reactant emulsion is generally
recycled in the process. The reactant emulsion may contain the
same, similar or different hydrocarbon fuel and/or emulsifier than
the aqueous hydrocarbon fuel. The reactant emulsion may be the
same, similar or different composition as the desired aqueous
hydrocarbon fuel emulsion. By using a reactant emulsion as an
initial component, the overall particle size decreases and the
aqueous hydrocarbon fuel emulsion stability is increased.
[0080] The hydrocarbon fuel and emulsifier contains about 50% to
about 99% by weight, preferably about 85% to about 98% by weight,
and more preferably about 95% to about 98% by weight hydrocarbon
fuel, and it further contains about 0.05% to about 25%, preferably
about 1% to about 15%, and more preferably about 1% to about 5% by
weight of at least one emulsifier.
[0081] Optionally, additives may be added to the reactant emulsion,
hydrocarbon fuel, emulsifier, water or combinations thereof. The
additives include but are not limited to cetane improvers, organic
solvents, antifreeze agents, surfactants, other additives known for
their use in fuel and the like. The additives are added to the
reaction emulsion, hydrocarbon fuel, emulsifier or the water, prior
to and in the alternative at the first emulsification step
dependent upon the solubility of the additive. The additives are
generally in the range of about 1% to about 40% by weight,
preferably about 5% to about 30% by weight, and more preferably
about 7% to about 25% by weight of the additive emulsifier.
[0082] The water can optionally include but is not limited to the
water-soluble additives such as antifreeze, ammonium nitrate,
ammonium salts or mixtures thereof. Ammonium nitrate is generally
added to the water mixture as an aqueous solution. In one
embodiment the water, the antifreeze and/or the ammonium nitrate
are mixed dynamically and fed continuously to the process. In
another embodiment the water, antifreeze, ammonium nitrate or
mixtures thereof flow out of separate tanks and/or combinations
thereof into or mixed prior to the first emulsification step. In
one embodiment the water, water alcohol, water-ammonium nitrate, or
water-alcohol ammonium nitrate mixture meets the hydrocarbon fuel
additives mixture immediately prior to or in the emulsification
step.
[0083] A programmable logic controller (plc) is optionally employed
for governing the continuous flow of the components, thereby
controlling the flow rates and mixing ratio in accordance with the
prescribed blending rates. The plc stores component percentages
input by the operator. The plc then uses these percentages to
define volumes/flow of each component required. Continuous flow
sequence is programmed into the plc. The plc electronically
monitors all level switches, valve positions and fluid meters.
EXAMPLE 5
[0084] This example is illustrative of making a hydrocarbon fuel
emulsion product by a continuous process. A mixture having the
following components was prepared.
3 Concentrate Emulsion Diesel -- 78.12 Water -- 20.00 Emulsifier 1
40.00 0.5 Emulsifier 2 7.14 0.214 Emulsifier 3 19.80 0.297
2-ethylhexylnitrate 23.80 0.714 Ammonium Nitrate 9.26 0.15 (54% by
weight in water Emulsifier 1: Reaction product of
dimethylethanolamine and PIBSA (Mn-2000) Emulsifier 2: Reaction
product of dimethylethanolamine and hexadecylsuccinnic anhydride
Emulsifier 3: Reaction product of an ethylene polyamine and PIBSA
(Mn-1000)
[0085] About 2.88% weight of an emulsifier reactant is added to
about 97.12% weight of diesel fuel and mixed to produce a
hydrocarbon fuel emulsifier mixture. The hydrocarbon fuel and
emulsifier, at a flow rate of 4.95 gallons per minute (F1), was
emulsified with water that had a flow rate of about 1.05 gallons
per minute (F2) at room temperature along with the emulsion
reactant that had a flow rate of about 6.0 gallons per minute (F4).
The processing streams were introduced close to the entry portal of
the shear mixer as possible. The shear mixer was a 12 GPM IKA Works
Dispax mixer with three superfine mixing elements operating at
about 9600 rpm (revolutions per minute). The output from this mixer
(F3) was then split into two streams where about 6.0 gallons per
minute was diverted through a conduit to the inlet of the IKA Works
Dispax mixer (F4) and about 6.0 gallons per minute was pumped
through a conduit to storage (F5). This process has been shown to
produce a water in oil emulsion with the following particle size
distribution (see FIG. 1).
[0086] The particle size of the resulting emulsion made by the
continuous process with an identical formulation made via a process
without the emulsion co-feed (i.e. F4=0 gallons per minute) is
shown in FIG. 2.
[0087] The example showed that a continuous process using an
emulsion co-feed unexpectedly consistently produced higher quality
results.
[0088] The aqueous hydrocarbon fuel emulsion product produced by
the continuous process involves less processing time than by batch
processing. Thus, the inventive process to make the same
water-blended fuel product is an improvement over other processes
because of the increased throughput and efficiency.
[0089] The Hydrocarbon Fuel
[0090] 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. 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.
[0091] 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.
[0092] 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.
[0093] The Water
[0094] 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.
[0095] 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.
[0096] The Reactant Emulsion Component
[0097] The reactant emulsion is at least one of the ingredients in
the process and not necessarily a reactant in a chemical reaction.
The reactant emulsion comprises the hydrocarbon fuel, water and at
least one emulsifier. The reactant emulsion may be prepared by the
steps of (1) mixing the fuel and an emulsifying amount of at least
one emulsifier using standard mixing techniques to form the initial
emulsion component or, in the alternative, under emulsification
mixing conditions to form the reactant emulsion. The reactant
emulsion can be prepared from any emulsion process including the
process of this invention. It is in effect a recycling of a
finished emulsified fuel into the process for making more
emulsifier fuels.
[0098] The initial emulsion component contains about 50% to about
99% by weight, in another embodiment about 85% to about 98% by
weight, and in another embodiment about 95% to about 98% by weight
hydrocarbon fuel, and it further contains about 0.05% to about 25%,
in another embodiment about 1% to about 15%, and in another
embodiment about 1% to about 5% by weight of the emulsifier.
[0099] The reactant emulsifier can have the same, similar or a
different emulsifier and the same, similar or different fuel then
is used to form the aqueous hydrocarbon fuel emulsion. The
emulsifier includes but is not limited to:
[0100] (i) at least one fuel-soluble product made by reacting at
least one hydrocarbyl-substituted carboxylic acid acylating agent
with ammonia or an amine including but not limited to alkanol
amine, hydroxy amine, and the like, the hydrocarbyl substituent of
said acylating agent having about 50 to about 500 carbon atoms;
[0101] (ii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0102] (iii) mixture of (ii) with (i);
[0103] (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;
[0104] (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, an alkanol amine or hydroxy
amines;
[0105] (vi) an amino alkylphenol which is made by reacting an
alkylphenol, an aldehyde and an amine resulting in an amino
alkylphenol, or
[0106] (vii) the combination of (vi) with (i), (ii), (iii), (iv),
(v) or combinations thereof.
[0107] The Emulsifier
[0108] Fuel Soluble Product (i)
[0109] 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.
[0110] 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.
[0111] The hydrocarbyl-substituted carboxylic acid acylating agents
may be made by reacting one or more alpha-beta olefinically
unsaturated carboxylic acid reagents containing 2 to about 20
carbon atoms, exclusive of the carboxyl groups, with one or more
olefin polymers as described more fully hereinafter.
[0112] 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.
[0113] 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.
[0114] 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.
[0115] The amines include but are not limited to hydroxyamines,
such as mono-, di-, and triethanolamine, dimethylethanol amine,
diethylethanol amine, di-(3-hydroxy propyl) amine,
N-(3-hydroxybutyl) amine, N-(4-hydroxy butyl) amine, and
N,N-di-(2-hydroxypropyl) amine; alkylene polyamines such as
methylene polyamines, ethylene polyamines, butylene polyamines,
propylene polyamines, pentylene polyamines, and the like. Specific
examples of such polyamines include ethylene diamine, diethylene
triamine, triethylene tetramine, propylene diamine, trimethylene
diamine, tripropylene tetramine, tetraethylene pentamine,
hexaethylene heptamine, pentaethylene hexamine, or a mixture of two
or more thereof; ethylene polyamine; 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.
[0116] The fuel-soluble product (i) may be present in the
water-fuel emulsion at a concentration of up to about 15% by weight
based on the overall weight of the emulsion, and in one embodiment
about 0.1 to about 15% by weight, and an one embodiment about 0.1
to about 10% by weight, and in one embodiment about 0.1 to about 5%
by weight, and in one embodiment about 0.1 to about 2% by weight,
and in one embodiment about 0.1 to about 1% by weight, and in one
embodiment about 0.1 to about 0.7% by weight.
[0117] The Ionic or Nonionic Compound (ii)
[0118] 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. Examples include low
molecular weight variants of (i) or (vii) such as those having a
hydrocarbon group in the range of C.sub.8 or C.sub.20. Useful
compounds include 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.
[0119] Emulsifier Mixture (iii)
[0120] 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.
[0121] The Water-Soluble Compound (in iv)
[0122] 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.
[0123] 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.
[0124] The water-soluble compound may be present in the water-fuel
emulsion at a concentration of about 0.001 to about 1% by weight,
and in one embodiment from about 0.01 to about 1% by weight.
[0125] Emulsifier (v)
[0126] 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.
[0127] 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.
[0128] 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 alpha-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, C.sub.18-30 alpha-olefins, and the like. Mixtures of
two or more of any of the foregoing alpha-olefins or alpha-olefin
fractions may be used.
[0129] 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.
[0130] In another embodiment the polyacidic polymer is a copolymer
of an olefin and a monomer having the structure: 1
[0131] 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.
[0132] 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.
[0133] 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.
[0134] Amino Alkylphenol Emulsifier (vi) and (vii)
[0135] The amino alkyl emulsifier is comprised of the reaction
product of an amino alkylphenol, an aldehyde, and an amine
resulting in amino alkylphenol. The amino alkylphenol can be made
by (a) the reaction of alkylphenol directly with an aldehyde and an
amine resulting in an alkylphenol monomer connected by a methylene
group to an amine, (b) the reaction of an alkylphenol with an
aldehyde resulting in an oligomer wherein the alkylphenols are
bridged with methylene groups, the oligomer is then reacted with
more aldehyde and an amine to give a Mannich product, or (c) a
mixture of (a) and (b) 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.
[0136] 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.
[0137] 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.
[0138] 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.)
[0139] 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 2
[0140] or alkenyl succinic acid such as succinic acids of the
formula 3
[0141] with the amines of the foregoing paragraph.
[0142] 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.
[0143] 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. The reaction
temperature is in the range of about 40.degree. C. to about
200.degree. C., preferably about 50.degree. C. to about 160.degree.
C., and more preferably about 60.degree. C. to about 150.degree. C.
The reaction may be carried out at elevated or reduced pressure,
but is preferably carried out at atmospheric pressure. The reaction
is generally carried out over a period of time in the range of
about 15 minutes to about 8 hours, preferably about 1 hour to about
6 hours, and more preferably about 2 hours to about 4 hours.
[0144] The amino alkylphenols emulsifier of this invention may be
made by reacting the alkylphenol:aldehyde:amine in a ratio range of
1:1:0.1 molar to 1:2:2 molar, in one embodiment preferably
1:0.9:0.1 to 1:1.9:1.9, in one embodiment preferably 1:1.5:1.2
molar to 1:1.9:1.8 molar, and in one embodiment preferably
1:0.8:0.3 to 1:1.5:0.7, resulting in the amino alkylphenol
emulsifier.
[0145] Ranges for the emulsifier treated in the water blend fuel
are in the concentration of about 0.05% to about 20% by weight, and
in another embodiment 0.05% to about 10% by weight, and in another
embodiment about 0.1% to about 5%, and in another embodiment 0.1%
to about 3% by weight of the total emulsion.
[0146] In another embodiment of this invention the amino
alkylphenol is made by the reaction of an alkylphenol with an
aldehyde, resulting in an oligomer wherein the alkylphenols are
bridged with methylene groups; then the oligomer is reacted with
more aldehyde and amine to give the emulsifier Mannich product of
this invention. The reaction is prepared by any known method such
as an emulsion, a solution, a suspension, and a continuous addition
bulk process. The reaction is carried out under conditions that
provide for the formation of the desired product.
[0147] The reaction is carried out at a temperature in the range of
about 0.degree. C. to about 150.degree. C., preferably to about
20.degree. C. to about 100.degree. C., and more preferably about
30.degree. C. to about 70.degree. C. over a period of time in the
range of about 15 minutes to about 8 hours, preferably about 1 hour
to about 6 hours, and more preferably about 2.5 hours to about 5
hours, resulting in an oligomer wherein the alkylphenols are
bridged with methylene groups. This intermediate product is then
reacted in the range of about 1 mole oligomer:0.1 mole amine to
about 1 mole oligomer:2 moles amine; preferably about 1 mole
oligomer:0.2 mole amine to about 1 mole oligomer:1.5 moles amines,
and more preferably about 1 mole oligomer:0.3 moles amine to about
1 mole oligomer:0.9 moles amine, resulting in amino alkylphenol
product.
[0148] This reaction occurs at a temperature of about 40.degree. C.
to about 200.degree. C., preferably about 50.degree. C. to about
160.degree. C., and more preferably about 60.degree. C. to about
150.degree. C. The reaction may be carried out at elevated to
reduced pressure, but is preferably carried out at atmospheric
pressure. The reaction continues until the Mannich product is
formed.
[0149] This embodiment is illustrated as follows: 4
[0150] The emulsifier may be a mixture of the amino alkylphenol
with
[0151] (i) at least one fuel-soluble product made by reacting at
least one hydrocarbyl-substituted carboxylic acid acylating agent
with ammonia or an amine, including, but not limited to, alkanol
amines, hydroxy amines, and the like, the hydrocarbyl substituent
of said acylating agent having about 50 to about 500 carbon
atoms;
[0152] (ii) at least one of an ionic or a nonionic compound having
a hydrophilic-lipophilic balance (HLB) of about 1 to about 40;
[0153] (iii) mixture of (ii) with (i);
[0154] (iv) a water-soluble compound selected from the group
consisting of amine salts, ammonium salts, azide compounds, nitrate
esters, nitramine, nitro compounds, alkali metal salts, alkaline
earth metal salts, in combination with at least one of (i), (ii),
(iii), (v), (vii) or combinations thereof;
[0155] (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 amines, or hydroxy amines;
or
[0156] (vi) combinations thereof.
[0157] The emulsifier may be present in the water 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 water fuel
emulsion.
[0158] Cetane Improver
[0159] In one embodiment, the water-fuel emulsion contains a cetane
improver. The cetane improvers that are useful include but are not
limited to peroxides, nitrates, nitrites, nitrocarbamates, and the
like. Useful cetane improvers include but are not limited to
nitropropane, dinitropropane, tetranitromethane,
2-nitro-2-methyl-1-butanol, 2-methyl-2-nitro-1-propanol, and the
like. Also included are nitrate esters of substituted or
unsubstituted aliphatic or cycloaliphatic alcohols which may be
monohydric or polyhydric. These include substituted and
unsubstituted alkyl or cycloalkyl nitrates having up to about 10
carbon atoms, and in one embodiment about 2 to about 10 carbon
atoms. The alkyl group may be either linear or branched, or a
mixture of linear or branched alkyl groups. Examples include methyl
nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl
nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate,
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.
[0160] The concentration of the cetane improver in the water-fuel
emulsion may be 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.
[0161] Additional Additives
[0162] In addition to the foregoing materials, other fuel additives
that are well known to those of skill in the art may be used in the
water-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.
[0163] The total concentration of chemical additives, including the
foregoing emulsifiers, in the water-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.
[0164] Organic Solvent
[0165] 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 water-fuel emulsion.
[0166] The water-fuel emulsions 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.
[0167] Antifreeze Agent
[0168] 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.
[0169] The Engines
[0170] 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.
* * * * *