U.S. patent application number 10/470426 was filed with the patent office on 2004-04-15 for fuel additive composition and fuel composition and method thereof.
Invention is credited to Barbour, Robert H., Duncan, David A., Moreton, David J..
Application Number | 20040068922 10/470426 |
Document ID | / |
Family ID | 32070069 |
Filed Date | 2004-04-15 |
United States Patent
Application |
20040068922 |
Kind Code |
A1 |
Barbour, Robert H. ; et
al. |
April 15, 2004 |
Fuel additive composition and fuel composition and method
thereof
Abstract
A fuel additive composition includes a reaction product of a
succinic acylating agent and a polyamine having at least one
condensable primary amine group where the reaction product has a
ratio of the imide to amide infrared carbonyl absorption peak areas
of about 1:0.0-0.6 and a water content of about 0.3% or less by
weight. The succinic acylating agent is prepared by thermal
condensation of a highly reactive polyolefin with maleic anhydride
or a reactive equivalent thereof. This fuel additive composition
has a low chlorine content and is very effective in fuel
compositions that include a normally liquid fuel in reducing
deposits in the fuel intake system of an internal combustion
engine.
Inventors: |
Barbour, Robert H.;
(Derbyshire, GB) ; Duncan, David A.; (Derbyshire,
GB) ; Moreton, David J.; (Derbyshire, GB) |
Correspondence
Address: |
Jeffrey F Munson
The Lubrizol Corporation
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Family ID: |
32070069 |
Appl. No.: |
10/470426 |
Filed: |
July 28, 2003 |
PCT Filed: |
February 13, 2002 |
PCT NO: |
PCT/US02/04167 |
Current U.S.
Class: |
44/418 ; 44/419;
44/420; 44/421 |
Current CPC
Class: |
C10L 10/18 20130101;
C10L 10/04 20130101; C10L 1/224 20130101; C10L 1/143 20130101; C10L
1/1616 20130101; C10L 1/221 20130101; C10L 1/19 20130101; C10L
1/2383 20130101 |
Class at
Publication: |
044/418 ;
044/419; 044/420; 044/421 |
International
Class: |
C10L 001/24; C10L
001/22 |
Claims
What is claimed is:
1. A fuel additive composition, comprising: a reaction product of
an aliphatic hydrocarbon substituted succinic acylating agent and a
polyamine having at least one condensable primary amine group
represented by the formula --NH.sub.2 wherein said reaction product
has a ratio of the imide to amide infrared carbonyl absorption peak
areas of about 1:0.0-0.6 and a water content of about 0.3% or less
by weight, and wherein the aliphatic hydrocarbon substituted
succinic acylating agent is prepared by thermal condensation of a
highly reactive polyolefin with maleic anhydride or a reactive
equivalent thereof.
2. The composition of claim 1 wherein the reaction product has a
ratio of the imide to amide infrared carbonyl absorption peak areas
of about 1:0.0-0.4 and a water content of about 0.25% or less by
weight.
3. The composition of claim 1 wherein the reaction product has a
ratio of the imide to amide infrared carbonyl absorption peak areas
of about 1:0.0-0.3 and a water content of about 0.2% or less by
weight.
4. The composition of claim 1 wherein the reactive polyolefin
contains about 30 to about 180 carbon atoms and is derived from
homopolymerized or interpolymerized 1-olefins having 2 to 18 carbon
atoms.
5. The composition of claim 1 wherein the reactive polyolefin is a
polyisobutylene having a number average molecular weight of about
400 to about 2,500.
6. The composition of claim 1 wherein the polyamine is selected
from the group consisting of ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyethylene polyamine bottoms, and mixtures
of two or more thereof.
7. The composition of claim 1 wherein the polyamine is
tetraethylenepentamine.
8. The composition of claim 6 wherein the reactive polyolefin is a
polyisobutylene.
9. The composition of claim 8 wherein the molar ratio of the
succinic acylating agent to the polyamine is about 1:0.5-1.
10. The composition of claim 1 further comprising a carrier
fluid.
11. The composition of claim 10 wherein the carrier fluid is an oil
having a viscosity of about 100 to about 400 centistokes at
40.degree. C.
12. The composition of claim 1 further comprising a solvent.
13. The composition of claim 12 wherein the solvent is an aliphatic
hydrocarbon, aromatic hydrocarbon or mixtures thereof.
14. A fuel composition comprising a major amount of a normally
liquid fuel that is a gasoline or a diesel fuel; and the fuel
additive composition of claim 1.
15. The fuel composition of claim 14 wherein the diesel fuel is a
hydrocarbon diesel fuel, a biodiesel fuel, or a mixture
thereof.
16. The fuel composition of claim 14 wherein the reaction product
of the succinic acylating agent and the polyamine ranges from about
10 ppm to about 1,000 ppm based on the weight of the fuel
composition.
17. A method of reducing deposits in the fuel intake system of an
internal combustion engine by operating the engine with the fuel
composition of claim 14.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention involves fuel additive compositions, fuel
compositions that include the fuel additive compositions, and a
method of operating internal combustion engines with the fuel
compositions. The compositions of the present invention are
effective in reducing deposits in fuel intake systems of internal
combustion engines.
[0003] 2. Description of the Related Art
[0004] Deposits form in the fuel intake system of an internal
combustion engine and can adversely affect combustion performance
in terms of power output and emissions. Fuel additives are
generally incorporated into a fuel to reduce deposits and maintain
satisfactory engine performance. Fuel additives that are improved
in reducing deposits are advantageous.
[0005] Hydrocarbon substituted succinimides, derived from a
succinic acylating agent which is prepared by thermal condensation
of a highly reactive polyisobutylene with maleic anhydride or a
reactive equivalent thereof, provide deposit reduction performance
in fuel compositions and have a low chlorine content which is an
environmental feature now required in Europe.
[0006] U.S. Application Serial No. 60/219,791 filed Jul. 19, 2000
(Duncan et al.) disclose an additive composition comprising the
combination of a succinimide and an oil, having a viscosity of 100
to 400 centistokes at 40.degree. C., that can reduce fouling of
middle distillate fuel oil injectors in a compression ignition
engine.
[0007] International Publication No. WO 99/32585 published Jul. 1,
1999 (Moreton) discloses polyisobutene substituted succinimides
derived from N-aminoalkyl substituted imidazoles that are
detergents for use in fuels.
[0008] U.S. Pat. No. 5,925,151 filed Sep. 19, 1996 (DeCanio et al.)
disclose a detergent additive composition comprising the
combination of a monosuccinimide, derived from polyisobutylene and
a polyethylene polyamine, and an aromatic hydrocarbon diluent that
may be used in diesel fuel to remove or prevent deposits.
[0009] It has now been found that the succinimides of the present
invention, prepared by thermal condensation of a highly reactive
polyolefin with maleic anhydride or a reactive equivalent thereof
followed by amination of the thermal condensate with a polyamine
under conditions that increase imide content and decrease water
content, provide improved performance in fuel compositions in
reducing deposits in fuel intake systems of internal combustion
engines. The succinimides of the present invention also have the
environmental feature of a low chlorine content.
SUMMARY OF THE INVENTION
[0010] It is an object of this invention to reduce deposits in the
fuel intake system of an internal combustion engine fueled with a
normally liquid fuel.
[0011] It is a further object of this invention to reduce deposits
in the fuel intake system of a compression ignition engine fueled
with a diesel fuel.
[0012] The objects, advantages and embodiments of the present
invention are in part described in the specification and in part
are obvious from the specification or from the practice of the
invention. Therefore, it is understood that the invention is
covered as described or obvious that falls within the scope of the
appended claims.
[0013] To achieve the foregoing objects in accordance with the
invention as described and claimed herein, the fuel additive
composition of the present invention comprises a reaction product
of an aliphatic hydrocarbon substituted succinic acylating agent
and a polyamine having at least one condensable primary amine group
represented by the formula --NH.sub.2 wherein said reaction product
has a ratio of the imide to amide infrared carbonyl absorption peak
areas of about 1:0.0-0.6 and a water content of about 0.3% or less
by weight, and wherein the aliphatic hydrocarbon substituted
succinic acylating agent is prepared by thermal condensation of a
highly reactive polyolefin with maleic anhydride or a reactive
equivalent thereof.
[0014] A further embodiment of the present invention is a fuel
composition comprising a major amount of a normally liquid fuel
that is a gasoline or a diesel fuel; and the above-described fuel
additive composition.
[0015] Another aspect of the present invention is a method of
reducing deposits in the fuel intake system of an internal
combustion engine by operating the engine with the above-described
fuel composition.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The fuel additive compositions of the present invention
comprise a reaction product of an aliphatic hydrocarbon substituted
succinic acylating agent and polyamine.
[0017] The aliphatic hydrocarbon substituent of the succinic
acylating agent can be a straight- or branched-chain hydrocarbon
group, and can be saturated, olefinic with one or more
carbon-to-carbon double bonds, or acetylenic with a
carbon-to-carbon triple bond. The aliphatic hydrocarbon substituent
is usually a branched-chain, olefinic group.
[0018] The polyamine contains two or more amine groups where at
least one of the amine groups is a condensable primary amine group
represented by the formula --NH.sub.2.
[0019] The reaction product of the present invention of the
succinic acylating agent and polyamine has a ratio of the imide to
amide infrared carbonyl absorption peak areas of about 1:0.0-0.6
and a water content of about 0.3% or less by weight. The reaction
of the succinic acylating agent and polyamine can result in a
reaction product that contains several components including the
succinate derivatives imide, amide and ammonium carboxylate salt.
The reaction of the succinic acylating agent and polyamine is run
under conditions detailed herein that increases the amount of the
imide relative to the amide and ammonium carboxylate salt and that
decreases the water content of the reaction product.
[0020] The succinic acylating of the present invention is usually a
succinic anhydride, but can be a reactive equivalent to include the
bisacid, bisesters, and acid-esters and bis acyl halides. The
succinic acylating agent is prepared by a thermal condensation of a
highly reactive polyolefin with maleic anhydride or a reactive
equivalent thereof to include maleic acid, bis acyl halides,
bisesters and acid-esters. Maleic anhydride is generally used.
[0021] The highly reactive polyolefin used to prepare the succinic
acylating agent of the present invention contains a major amount of
its carbon to carbon double bonds in a terminal position on the
carbon chain as vinylidene type double bonds represented by the
formula 1
[0022] In one embodiment at least 70% of the double bonds in the
highly reactive polyolefin are vinylidene type, in another instance
at least 80% are vinylidene type, and in yet another instance at
least 90% are vinylidene type.
[0023] The highly reactive polyolefin can contain about 30 to about
180 carbon atoms, and in another instance about 40 to about 130
carbon atoms. The polyolefin usually contains about 55 to about 90
carbon atoms.
[0024] The highly reactive polyolefin can be derived from
homopolymerized or interpolymerized 1-olefins having 2 to 18 carbon
atoms. The 1-olefins include ethylene, propylene, the butene
isomers 1-butene, 2-butene and isobutylene, and mixtures of
1-olefins. Examples of polyolefins are polyethylenes,
polypropylenes, polyisobutylenes, especially those derived from
refinery streams, copolymers of ethylene and 1-olefins such as
ethylene-propylene copolymers, and terpolymers of ethylene with
1-olefins and dienes such as ethylene-propylene-diene
terpolymers.
[0025] A preferred highly reactive polyolefin is a polyisobutylene
having a high vinylidene content of 70% or more. The
polyisobutylene can have a number average molecular weight of about
400 to about 2,500, while about 600 to about 1,800 is more
preferred, and about 800 to about 1,200 is most preferred. Well
known procedures involving gel phase chromatography and vapor phase
osmometry are used to determine the number average molecular
weights of polyolefins such as polyisobutylene. Polyisobutylene
having a high vinylidene content is commercially available from
BASF under the tradename Glissopal.RTM..
[0026] The succinic acylating agents of the present invention are
prepared by thermally condensing a highly reactive polyolefin with
maleic anhydride or a reactive equivalent thereof. Procedures for
the thermal condensation are well known and usually involve
temperatures above 200.degree. C. at an elevated pressure. U.S.
Application Serial No. 60/219,791 filed Jul. 19, 2000 (Duncan et
al.) describe the procedure for a thermal condensation of a
polyisobutylene having a high vinylidene content with maleic
anhydride, the disclosure of which is incorporated herein by
reference. There is a two-fold advantage to preparing the succinic
acylating agent via a thermal condensation with a highly reactive
polyolefin. First, the thermal condensation provides a nonchlorine
route to the succinic acylating agents so that their succinimide
derivatives have a low chlorine content. Second, conversion of the
highly reactive polyolefins to hydrocarbon substituted succinic
acylating agents is high so that their succinimide derivatives have
a high active chemical content and are effective as fuel additives
in reducing deposits in fuel intake systems.
[0027] The polyamines of the present invention include polyethylene
polyamines as well as other types of polyamines. Polyethylene
polyamines are available from Dow and Union Carbide and include
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine and polyethylene
polyamine bottoms. Other types of polyamines include polyalkylene
polyamines in addition to polyethylene polyamines described above,
heterocyclic polyamines, aromatic heterocyclic polyamines,
polyamines containing one or more hydroxyl groups and ether or
polyether containing polyamines. Examples of other types of
polyamines are tris(2-aminoethyl)amine, propylenediamine,
dipropylenetriamine, N-(2-aminoethyl)-1,3-propanediamine,
N,N'-bis(2-aminoethyl)-1,3-propanediamine,
dimethylaminopropylamine, diethylaminopropylamine,
1-(3-aminopropyl) imidazole and 4-(3-aminopropyl) morpholine.
[0028] The succinic acylating agent and polyamine of the present
invention can be reacted using various molar ratios of the two
reactants. A preferred molar ratio of succinic acylating agent to
polyamine is about 1:0.3-1.1, more preferred is about 1:0.5-1, and
most preferred is about 1:0.74-1.
[0029] The present invention involves the reaction product of a
succinic acylating agent, derived from thermally condensing a
highly reactive polyolefin and maleic anhydride or a reactive
equivalent thereof, and a polyamine under reaction conditions
wherein the reaction product has an increased imide content and
decreased water content relative to analogous materials prepared
under conditions less selective for increased imide and decreased
water content. It has been found that increasing the level of imide
relative to amide and ammonium carboxylate salt in the reaction
product provides a fuel additive composition with improved deposit
reduction performance in the fuel intake system of an internal
combustion engine. Additionally, it has been found that decreasing
the level of water in the reaction product provides a fuel additive
composition that is much more stable and retains a nearly constant
imide level for a long period of time. In contrast, analogous
materials prepared under conditions less selective for increased
imide level and decreased water level provide a reduced level of
deposit reduction as fuel additives and also show a much greater
decrease in imide content with time. The additive composition of
the present invention provides improved deposit reduction
performance due to the increased imide content. Additionally, this
improved performance is deliverable even after a lengthy storage
period due to the decreased water content which results in a more
stable imide content with time.
[0030] The reaction products of the present invention have an
increased level of imide relative to amide and ammonium carboxylate
salt compared to analogous materials prepared under conditions less
favorable to forming imide such as current commercial materials.
The reaction products of the present invention have a ratio of the
imide to amide to ammonium carboxylate salt infrared carbonyl
absorption peak areas of about 1:0.0-0.6:0.0-0.3, more preferably
of about 1:0.0-0.4:0.0-0.2, and most preferably of about
1:0.0-0.3:0.0-0.1. The infrared carbonyl absorption peak areas were
obtained using a Perlin-Elmer "Spectrum One" program for imide at
about 1,705 cm.sup.-1, for amide at about 1,660 cm.sup.-1 and for
ammonium carboxylate salt at about 1,550cm.sup.-1. Samples of an
analogous commercial material prepared under conditions less
selective for imide formation had a ratio of the imide to amide to
ammonium carboxylate salt infrared carbonyl absorption peak areas
of about 1:0.8-1.4:0.3-0.5. This commercial material also provided
less deposit reduction performance compared to reaction products of
the present invention as detailed in examples that follow
herein.
[0031] The reaction products of the present invention have a
decreased level of water that provides a fuel additive composition
that is more stable in having a nearly constant level of imide for
several months. This enhanced stability of the imide level ensures
delivery of improved performance from the increased level of imide
even after a lengthy storage period. It is known that current
commercial succinimide materials, prepared under less rigorous
conditions for water removal, will over time decrease in imide
content and increase in amide and ammonium carboxylate salt
content. This decrease in imide content represents a loss in
deposit reduction performance since improved performance has been
found to be directly related to increased imide content. It has
been found that the reaction products of the present invention have
a nearly constant level of imide for about 3 months with the imide
level only slowly decreasing over extended periods when the water
content of the reaction products as determined by Karl Fischer
titration is about 0.3% or less by weight, more preferably about
0.25% or less by weight, and most preferably about 0.2% or less by
weight. Examples that follow illustrate the stability of the imide
content when water content is decreased.
[0032] The reaction products of the succinic acylating agents and
polyamines of the present invention are prepared under reaction
conditions that result in products having a ratio of the imide to
amide infrared carbonyl absorption peak areas of about 1:0.0-0.6
and a water content of about 0.3% or less by weight. The reaction
conditions that can increase imide content and decrease water
content are temperatures of about 140.degree. C. or higher for an
extended period of time, use of an inert gas sparge, use of reduced
pressure, use of a solvent that forms an azeotrope with water, and
combinations of two or more thereof. The following examples are
illustrative of reaction conditions that result in reaction
products of the present invention which have increased imide
content and decreased water content.
EXAMPLE A
Comparative
[0033] A commercial succinimide, Komad 303 available from MOL of
Hungary, has a ratio of imide to amide to ammonium carboxylate salt
infrared carbonyl absorption peak areas of 1:1.39:0.5. Komad 303 is
60% active chemical in a 350 neutral mineral oil. Komad 303 is
prepared by thermal condensation of a high vinylidene 1,000
molecular weight polyisobutene (BASF Glissopal.RTM. 1000) and a
maleic anhydride followed by amination with tetraethylenepentamine
in a molar ratio of about 1:0.87.
EXAMPLE B
Comparative
[0034] A commercial succinimide, Komad 303 from a batch different
from that of Example A, has a ratio of imide to amide to ammonium
carboxylate salt infrared carbonyl absorption peak areas of
1:0.78:0.3.
EXAMPLE C
[0035] A sample (1003.5 g) of the commercial succinimide of Example
A was placed in a flask fitted for distillation and heated with
stiring to 180.degree. C. Some foaming was observed. A vacuum was
gradually applied, and the sample was held at 180.degree. and a
reduced pressure of 49 mm Hg for 1 hour. The product residue
weighed 986.1 g, and the distillate was a yellow liquid weighing
7.25 g. The product had a nitrogen content of 2.71%, a total base
number of 74 (where base equivalents are expressed in terms of mg
of KOH per g of sample), and a ratio of imide to amide to ammonium
carboxylate salt infrared carbonyl absorption peak areas of
1:0.46:0.09.
EXAMPLE D
[0036] A sample (300 g) of the commercial succinimide of Example B
was placed in a flask fitted for distillation, heated with stirring
to 175.degree. C., and held at 175.degree. C. for 3 hours. The
sample was heated to 200.degree. C., and 60 ml of 2-ethyl-1-hexanol
was added. A vacuum was applied, and the sample and alcohol were
held at 200.degree. C. and a reduced pressure of 49 mm Hg for 1
hour. The product residue weighed 286.5 g. The distillate collected
was 60 ml of the alcohol and 3 ml of water. The product had a
nitrogen content of 2.51%, a total base number of 60 (as mg KOH per
g of sample), a water content of 0.05%, and a ratio of imide to
amide to ammonium carboxylate salt infrared carbonyl absorption
peak areas of 1:0.21:0.02.
EXAMPLE E
[0037] A sample (3.5 Kg) of an unfiltered polyisobutenylsuccinic
anhydride, derived from a thermal condensation of a high vinylidene
1,000 molecular weight polyisobutene (BASF Glissopal.RTM. 1000) and
maleic anhydride, and 2.333 Kg of a 330 neutral mineral oil were
blended together at 50.degree. C. for 0.5 hour. The blend was then
filtered through diatomaceous earth. A sample of the filtrate (5
Kg) was placed in a flask fitted for distillation and heated with
stirring under a nitrogen purge to 175.degree. C.
Tetraethylenepentamine (567.9 g at a molar ratio of succinic
anhydride to polyamine of 1:0.87) was added dropwise over 95
minutes. The reaction mixture was held at 175.degree. C. for 3
hours. Vacuum was applied, and the mixture was held at 175.degree.
C. and a reduced pressure of 49 mm Hg for 0.5 hour. Next 580 ml of
2-ethyl-1-hexanol was added, and the mixture was heated to
190.degree. C. and held at 190.degree. C. for 2.5 hours. A vacuum
was applied, and the mixture held at 190.degree. C. and a reduced
pressure of 49 mm Hg to remove the alcohol and additional water.
The distillate consisted of 580 ml of the alcohol and 18 ml of
water. The product residue had a nitrogen content of 3.0%, a total
base number of 83 (as mg KOH per g of sample), a water content of
0.25%, and a ratio of imide to amide to ammonium carboxylate salt
infrared carbonyl absorption peak areas of 1:0.44:0.06. The product
had a nearly constant imide level over a period of 98 days.
EXAMPLE F
[0038] A sample (180 parts by weight) of an unfiltered
polyisobutenylsuccinic anhydride, derived from a thermal
condensation of a high vinylidene 1,000 molecular weight
polyisobutene (BASF Glissopal.RTM. 1000) and maleic anhydride, and
120 parts by weight of a 330 neutral mineral oil were blended
together at 50.degree. C. for 0.5 hr. The blend was then filtered
through diatomaceous earth. The filtrate was placed in a reactor
fitted for distillation and heated with stirring to 110.degree. C.
Tetraethylenepentamine (31.8 parts at a molar ratio of succinic
anhydride to polyamine of 1:0.72) was added over 3 hours at
110-120.degree. C. The reaction mixture was heated to 175.degree.
C. over 6 hours, and was nitrogen sparged at 175.degree. C. for 4
hours. The aqueous distillate was 4.6 parts. The product residue
was 320.6 parts. The product had a nitrogen content of 3.36%, a
total base number of 85.5 (as mg KOH per g of sample), a water
content of 0.1%, and a ratio of imide to amide to ammonium
carboxylate salt infrared carbonyl absorption peak areas of
1:0.23:0.03. The product had a nearly constant imide level over a
period of 70 days.
EXAMPLE G
[0039] A sample (180 g) of an unfiltered polyisobutenylsuccinic
anhydride, derived from a thermal condensation of a high vinylidene
1,000 molecular weight polyisobutene (BASF Glissopal.RTM. 1000) and
maleic anhydride, and 120 g of Solvesso 150 (high boiling aromatic
solvent from Exxon Chemicals) were blended together for 0.5 hour.
The blend was filtered through diatomaceous earth. The filtrate was
placed in a flask fitted for distillation, and heated with stirring
to 175.degree. C. Tetraethylenepentamine (34.1 g at a molar ratio
of succinic anhydride to polyamine of 1:0.87) was added dropwise,
and the reaction mixture was held at 175.degree. C. for 4 hours.
The product residue was 275 g. The distillate was 5.8 ml of a
yellow liquid. The product had a nitrogen content of 3.83%, a total
base number of 124 (as mg KOH per g of sample), a water content of
0.19%, and a ratio of imide to amide to ammonium carboxylate salt
infrared carbonyl absorption peak areas of 1:0.24:0.04.
[0040] The fuel additive compositions of the present invention can
include a carrier fluid. Suitable carrier fluids are alkylphenols
including alkoxylated alkylphenols, esters of carboxylic acids
including polyol esters and vegetable oils, alkoxylated alcohols
including polyols, polyalkylene glycols, and mineral oils. Mineral
oils having a viscosity ranging from about 100 to about 400
centistokes at 40.degree. C. are especially useful.
[0041] In another embodiment of the present invention, the fuel
additive compositions can include a solvent. Suitable solvents are
aliphatic hydrocarbons, aromatic hydrocarbons, glycol ethers,
alcohols, and mixtures thereof.
[0042] The fuel additive compositions in a further embodiment of
the present invention can include additional fuel additives such as
cold flow improvers, pour point depressants, storage stabilizers,
corrosion inhibitors such as alkenylsuccinic acids, cetane
improvers, anti-knock additives, anti-static agents, biocidal
additives, smoke suppressants, other types of detergents, antifoam
agents including silicone fluids, lubricity additives such as tall
oil fatty acid, and demulsifiers such as alkoxylated
alkylphenols.
[0043] Another embodiment of the present invention is a fuel
composition comprising a major amount of a normally liquid fuel and
the fuel additive composition of the present invention. The
normally liquid fuel can be a gasoline or a diesel fuel. The
gasoline can be one or more hydrocarbon fractions generally boiling
in the range from 30.degree. C. to 230.degree. C. The gasoline can
contain oxygenates, oxygen-containing compounds, including alcohols
such as ethanol and ethers such as methyl t-butyl ether. The diesel
fuel can be a hydrocarbon diesel fuel from one or more hydrocarbon
fractions generally boiling in the range from 140.degree. C. to
400.degree. C., for example, from 170 to 350.degree. C. The
hydrocarbon diesel fuel usually contains several hydrocarbon
fractions. In one embodiment the hydrocarbon diesel fuel has at
least 90% by volume hydrocarbon fraction boiling at 350.degree. C.,
in a second embodiment greater than 95% by volume fraction boiling
at 350.degree. C., in a third embodiment at least 10% by volume
fraction boiling at 180.degree. C., and in a fourth embodiment at
least 15% by volume fraction boiling at 180.degree. C. The aromatic
content of the hydrocarbon diesel fuel is typically less than 40%
by volume, in another instance less than 30%, and in a further
instance less than 20%. The cetane number of the hydrocarbon diesel
fuel is usually greater than 40, in another embodiment greater than
45, and in a further embodiment greater than 50. The sulfur content
of the hydrocarbon diesel fuel can be 0.5 wt % or less, in a second
instance 0.2 wt % or less, and in a third instance 0.05 wt % or
less, and in a fourth instance 0.0010 wt % or less. The diesel fuel
can be a biodiesel fuel. The biodiesel fuel includes esters of
naturally occurring fatty acids which can be prepared by the
transesterification of triglycerides of natural fats and oils with
lower aliphatic alcohols to include methyl, ethyl, propyl and butyl
alcohol. Natural fats and oils include sunflower oil, rapeseed oil,
coriander oil, castor oil, soybean oil, cottonseed oil, peanut oil,
coconut oil, and beef tallow. The diesel fuel can be a mixture of a
hydrocarbon diesel fuel and a biodiesel fuel such as the methyl
ester of rapeseed oil. Fuel compositions of the present invention
that include a diesel fuel are especially useful in compression
ignition engines to reduce deposits in the fuel intake system.
[0044] Fuel compositions of the present invention include the
reaction products of the succinic acylating agents and the
polyamines at a level sufficient to provide deposit reduction
performance. The level of the reaction product in the fuel
composition can range from about 10 ppm to about 1,000 ppm based on
the weight of the fuel composition, in another instance from about
20 ppm to about 600 ppm, and also from about 30 ppm to about 300
ppm.
[0045] The fuel additive compositions and fuel compositions of the
present invention are prepared by mixing components at ambient
temperatures or at somewhat elevated temperatures ranging from
about 40.degree. C. to 60.degree. C. until the mixture is
homogeneous. The components can include the reaction products of
the succinic acylating agents and polyamines, carrier fluids,
solvents, additional fuel additives, and normally liquid fuels.
[0046] A further embodiment of the present invention is a method of
reducing deposits in the fuel intake system of an internal
combustion engine by operating the engine with the fuel composition
of the present invention. This method is especially effective in
compression ignition engines fueled with diesel fuels in reducing
deposits in and around fuel injector nozzles. This deposit
reduction performance includes both preventing deposits from
forming as well as removing or cleaning up deposits that have
formed.
[0047] The following examples show the benefit of the present
invention in providing improved deposit reduction performance in
the fuel intake system of an internal combustion engine.
1 Peugeot XUD-9 Diesel Engine Test.sup.1 Imide to Amide Treat,
Average % Flow Detergent Ratio.sup.3 ppm.sup.4 Remaining.sup.1
Example A 1:0.87 100 31 (comparative) Example C 1:0.46 100 34
Example B 1:0.78 80 28 (comparative) Example E 1:0.44 80 38 Example
B 1:0.78 80 32 (comparative) Example D 1:0.21 80 37 Example F
1:0.23 80 38 Example G 1:0.24 80 44 Komad 303.sup.5 1:1.3 .sup.
60.sup.7 32 (comparative) (biodiesel) High Imide 1:0.03 .sup.
60.sup.7 36 Succinimide.sup.6 (biodiesel) .sup.1The Peugeot XUD-9
diesel engine 10 hour test is used to evaluate the effectiveness of
a detergent that is added to a diesel fuel as part of a diesel fuel
additive package. The test evaluates deposit reduction performance
of the detergent by measuring the average % flow remaining for the
fuel injectors at the end of test. Detergents having larger % flow
remaining values are more effective. .sup.2The detergents are the
succinimide compositions of Examples A-G that were described in
detail earlier in the detailed description. Examples A and B are
comparative while Examples C-G are embodiments of the present
invention showing improved deposit reduction performance.
.sup.3Ratios are determined as the ratio of infrared carbonyl
absorption peak areas for the imide at about 1,705 cm.sup.-1 and
for the amide at about 1,660 cm.sup.-1 using a Perkin-Elmer
"Spectrum One" program. .sup.4The treat levels are active chemical
levels of the detergents in the diesel fuel. .sup.5Komad 303 is a
commercial succinimide available from MOL of Hungary. .sup.6The
high imide succinimide was prepared by the procedure of Example F.
.sup.7The fuel consisted of 70% by volume of a standard hydrocarbon
diesel fuel and 30% by volume of a biodiesel fuel which was the
methyl ester of rapeseed oil.
[0048]
2 Cuminins L-10 Injector Deposit Test.sup.1 Detergent Imide to
Amide Ratio.sup.2 Deposit Rating.sup.3 Komad 303.sup.4 1:0.78 12.5
(comparative) Komad 303.sup.4 between 1:0.78 15.2 (comparative) and
1:1.3.sup.5 Example F between 1:0.23 8.4 and 1:0.48.sup.5
.sup.1Cummins L-10 fuel injector deposit test uses two Cummins L-10
diesel engines mounted in tandem configuration with one engine
operated to drive the second nonoperated engine in a test cycle
capable of producing injector deposits. U.S. Pat. No. 6,042,626
further describes the procedure, and test details are available
from Engineering Test Services, a division of the Cummins Engine
Co., Charleston, S.C., U.S.A. In the test standard # hydrocarbon
diesel fuel was treated with each detergent at the same commercial
treat level on an active chemical basis. .sup.2Ratios are
determined as the ratio of infrared carbonyl absorption peak areas
for imide at about 1,705 cm.sup.-1 and for the amide at about 1,660
cm.sup.-1 using a Perkins-Elmer "Spectrum One" program. .sup.3An
average deposit rating of 10 or lower for the fuel injectors is a
good, desirable result. .sup.4Komad 303 is a commercial succinimide
available from MOL of Hungary. .sup.5Infrared analyses of the
detergent were available for dates that bracketed the test
date.
* * * * *