Note: Descriptions are shown in the official language in which they were submitted.
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Title: FUEL COMPOSITION CONTAINING DETERGENT COMBINATION
AND METHODS THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention
This invention involves a fuel composition that includes a combination of
detergents
and methods that utilize the fuel composition to operate and to control
deposits in an
internal combustion engine.
Description of the Related Art
Hydrocarbon fuels generally contain substances that tend to foam deposits in
the fuel delivery system of an internal combustion engine such as the fuel
injectors
in diesel engines and the intalce valves in gasoline engines. These deposits,
if
allowed to build up, can significantly reduce engine performance in terms of
power
output, fuel economy and exhaust emissions. It is highly desirable to
incorporate
detergents into hydrocarbon fuels that are effective in controlling deposits
by
inhibiting their formation and facilitating their removal so that engine
performance
is maintained or improved.
Graiff et al. in European Publication No. EP 534551A1 published on March
31, 1993 disclose a gasoline composition that comprises a gasoline and a
mixture of
a) a polyamine selected from the group consisting of an aliphatic alkylene
polyamine containing at least one olefinic polymer, a Mannich polyamine, and
mixtures of the aliphatic alkylene polyamine and the Mannich polyamine and b)
a
hydrocarbyl poly(oxyallcylene) aminocarbamate.
Cunningham et al. in U.S. Patent No. 5,679,116 issued October 21, 1997
disclose fuel additive compositions comprising a) at least one
detergent/dispersant
which is a derivative of a hydrocarbon-substituted dicarboxylic acid or
anhydride, a
hydrocarbon having a polyamine attached, andlor a Mannich condensation
product,
b) a cyclopentadienyl complex of a transition metal and c) a liquid carrier or
additive
induction aid.
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Croudace et al. in International Publication No. WO 90/10051 published
September 7, 1990 disclose a fuel composition comprising a gasoline and an
additive combination comprising one or more C~+ primary amines, one or more
gasoline dispersants selected from the group consisting of polyalkylamines and
Mannich bases, and a fluidizer oil.
Daly in U.S. Patent No. 5,873,917 issued February 23, 1999 discloses a fuel
composition comprising a gasoline, a polyether alcohol, a hydrocarbylphenol,
and
optionally a third component comprising a nitrogen-containing dispersant to
include
hydrocarbyl-substituted amines, Mannich dispersants, and polyetheramines.
Wright in U.S. Patent No. 5,169,410 issued December 8, 1992 discloses a
method to stabilize gasoline mixtures comprising adding to the gasoline a
combination of a phenylenediamine having at least one N-H group and a strongly
basic organo-amine comprising a Mannich reaction product.
The present invention is directed to a fuel composition that includes a
combination of two nitrogen-containing detergents and that is unexpectedly
much
more effective and efficient in controlling deposits in a hydrocarbon fueled
internal
combustion engine compared to fuel compositions that include a combination of
either nitrogen-containing detergent with a fluidizer.
SUMMARY OF THE INVENTION
It is an object of the present invention to control deposits in an internal
combustion engine so that engine performance is maintained or improved.
An additional object of this invention is to control deposits in a gasoline
engine.
Another object of this invention is to control deposits in a diesel engine.
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 this invention. Therefore, it is understood that the invention
is
claimed as described or obvious as falls within the scope of the appended
claims.
To achieve the foregoing objects in accordance with the invention as
described and claimed herein, a fuel composition of this invention useful for
a spark
or a compression ignition internal combustion engine comprises a hydrocarbon
fuel,
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a combination of nitrogen-containing detergents comprising a hydrocarbyl-
substituted polyamine and a Mannich reaction product of an alkyl-substituted
hydroxyaromatic compound with an aldehyde and a polyamine having at least one
reactive N H group, and optionally a fluidizer comprising a polyether, a
polyetheramine, or mixtures thereof where the weight ratio of the hydrocarbyl-
substituted polyarnine to the Mannich reaction product is about 0.2:1 to
1:0.2, where
each of the nitrogen-containing detergents is present at about 20-100 ppm by
weight,
and where the weight ratio of the fluidizer to the combination of nitrogen-
containing
detergents is less than 0.5
Another embodiment of this invention is a method of operating an internal
combustion engine which comprises fueling the engine with the fuel composition
of
this invention where the hydrocarbon fuel is a gasoline or a diesel fuel, and
where
the gasoline or diesel fuel optionally contains an oxygenate comprising
methanol,
ethanol, methyl tent-butyl ether, ethyl tent-butyl ether, methyl tent-amyl
ether, or
mixtures thereof.
A further embodiment of this invention is a method of controlling deposits in
an internal combustion engine which comprises fueling the engine with the fuel
composition of this invention where the hydrocarbon fuel is a gasoline or a
diesel
fuel, and where the gasoline or diesel fuel optionally contains an oxygenate
comprising methanol, ethanol, methyl tert-butyl ether, ethyl tert-butyl ether,
methyl
tent-amyl ether, or mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
A fuel composition of the present invention useful for a spark or a
compression
ignition internal combustion engine comprises a hydrocarbon fuel; a
combination of
nitrogen-containing detergents comprising a hydrocarbyl-substituted polyamine
and
a Mannich reaction product of an allcyl-substituted hydroxyaromatic compound,
an
aldehyde and a polyamine having at least one reactive N-H group; and
optionally a
fluidizer comprising a polyether, a polyetheramine, or mixtures thereof where
the
weight ratio of the hydrocarbyl-substituted polyamine to the Mannich reaction
product is about 0.2:1 to 1:0.2, each of the nitrogen-containing detergents is
present
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at about 20-100 ppm by weight, and the weight ratio of the fluidizer to the
combination of nitrogen-containing detergents is less than 0.5
The hydrocarbon fuel of the present invention is well known to those skilled
in the art. Hydrocarbon fuels are generally derived from petroleum by various
refinery processes. The hydrocarbon fuel can be a gasoline or a diesel fuel.
The
gasoline or diesel fuel optionally can contain an oxygenate or oxygen-
containing
molecule up to a level of about 25°7o by weight of oxygenate.
Oxygenates include
alcohols, ethers, ketones, esters, nitroalkanes, or mixtures thereof. Commonly
used
oxygenates include methanol, ethanol, methyl tert-butyl ether, ethyl tert-
butyl ether,
methyl tert-amyl ether, or mixtures thereof. Gasoline, suitable for use in
spark
ignition engines, generally boils in the range from 30 to 230°C and has
a research
octane number typically in the range of about 90 to 100. Diesel fuel, suitable
for use
in compression ignition engines, generally boils in the range from 140 to
400°C and
has a cetane number in the range from 25 to 60.
The hydrocarbyl-substituted polyamine of the present invention has a
hydrocarbyl substituent with a number average molecular weight of about 500 to
5000, preferably about 700 to 2000, and more preferably about 900 to 1500. The
hydrocarbyl substituent is a univalent radical of carbon atoms that is
predominantly
hydrocarbon in nature but can have nonhydrocarbon substituent groups to
include
hydroxy groups and can contain heteroatoms. The hydrocarbon substituent can be
derived from a polyolefin having a number average molecular weight as
described
above for the hydrocarbyl substituent. The polyolefin can be a homopolymer
derived from one olefin or a copolymer derived from two or more olefins. The
olefin can have 2 to about 10 carbon atoms and includes ethylene, propylene,
butene
isomers, decene isomers, and mixtures of two or more thereof. The polyolefin
includes polyethylenes, polypropylenes, polybutenes and copolymers of ethylene
and propylene. A preferred polyolefin is a polyisobutylene prepared by
polymerization of a refinery stream containing about 30 to 60% by weight
isobutylene using a Lewis acid catalyst such as aluminum trichloride or boron
trifluoride. The polyolefin can be a polyisobutylene having at least
70°l0 of its olefin
double bonds at a terminal position on the carbon chain as the highly reactive
vinylidene isomer which is also described below for the Mannich reaction
product.
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The polyamine portion of the hydrocarbyl-substituted polyamine of the
present invention is derived from a polyamine containing two or more amine
nitrogen atoms and having at least one reactive N-H group. The polyamine can
be
aliphatic, cycloaliphatic, heterocyclic or aromatic and includes
alkylenediamines,
polyalkylenepolyamines, and hydroxy-containing polyamines. Polyamines that can
be used in preparing the hydrocarbyl-substituted polyamine include
ethylenediamine, 1,3-propylenediamine, N,N-di-methyl-1,3-propanediamine, N-
aminoethylpiperazine, N-aminopropylmorpholine, N,N'-di-butyl-para-phenylene-
diamine, diethylenetriamine, triethylenetetramine, 2-(2-
aminoethylamino)ethanol,
and mixtures thereof. In another instance the hydrocarbyl-substituted
polyamine is
derived from the group consisting of ethylenediamine, diethylenetriamine, N,N-
dimethyl-1,3-propanediamine, 2-(2-aminoethylamino)ethanol, and mixtures
thereof.
The hydrocarbyl-substituted polyamine can be prepared from the polyolefin
and the polyamine as detailed above by several methods as described in U.S.
Patent 6,193,767 to include 1) halogenating a polyolefin followed by reaction
with a
polyamine, 2) hydroformulating a polyolefin followed by reaction with a
polyamine
and finally hydrogenation of the aldehyde-polyamine reaction intermediate, and
3)
epoxidizing a polyolefin followed by reductive amination or amination with a
polyamine to form a polyamine or hydroxy-containing polyamine derivative
respectively. A preferred method of preparation involves chlorinating a
polyisobutylene so that it contains at least one chlorine atom. The
chlorinated
polyisobutylene is then reacted with the polyamine generally at elevated
temperatures of about 120°C or higher. A solvent can be used to
facilitate the
reaction. Excess polyamine can be used to avoid cross-linking to include dimer
formation as well as aid in hydrogen chloride removal although an inorganic
base
such as sodium hydroxide or sodium carbonate is usually employed to remove the
hydrogen chloride. U.S. Patent 5,407,453 describes the method of halogenating
a
polyolefin followed by reaction with a polyamine.
The Mannich reaction product of the present invention is derived from the
reaction of an alkyl-substituted hydroxyaromatic compound, an aldehyde, and a
polyamine having at least one reactive N-H group. The hydroxyaromatic portion
of
the alkyl-substituted hydroxyaromatic compound comprises phenol, ortho-cresol,
or
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mixtures thereof. The alkyl-substituent of the alkyl-substituted
hydroxyaromatic
compound can be derived from a polyolefin which can be a homopolymer,
copolymer, or mixtures thereof. The polyolefin can have a number average
molecular weight of about 200 to 5000, preferably about 300 to 3000, and more
preferably about 400 to 1500. In one instance the polyolefin can have a number
average molecular weight of about 400 to 700 and in another instance about 900
to
1500. These polyolefins can be prepared from olefin monomers of 2 to about 10
carbon atoms to include ethylene, propylene, isomers of butene, isomers of
decene
and mixtures of two or more thereof. The polyolefins include polyethylenes,
polypropylenes, polybutenes and copolymers of ethylene and propylene. A
preferred polyolefin is a polyisobutylene derived from a refinery stream
having an
isobutylene content of about 30 to 60% by weight. A more preferred polyolefin
is a
polyisobutylene having at least 70% of its olefinic double bonds at a temninal
position on the carbon chain as the vinylidene type. Highly reactive
polyisobutylenes having a high vinylidene isomer content include Glissopal"
marketed by BASF. The alkyl-substituted hydroxyaromatic compound can be
prepared by well known methods including alkylating a hydroxyaromatic compound
such as phenol with a polyolefin such as polyisobutylene using a Lewis acid
catalyst
like boron trifluoride.
The aldehyde used to prepare the Mannich reaction product of the present
invention can be an aldehyde having 1 to about 6 carbon atoms. Formaldehyde is
preferred and can be used in one of its reagent forms such as paraformaldehyde
and
formalin.
The polyamine used to prepare the Mannich reaction product of the present
invention contains at least two or more amine nitrogen atoms and has at least
one
reactive N-H group capable of undergoing the Mannich reaction . The polyamine
includes alkylenediamines, polyalkylenepolyamines, polyamines containing
hydroxy
groups and cyclic polyamines. The Mannich reaction product can be derived from
the group consisting of ethylenediamine, propylenediamine, N,N-dimethyl-
ethylenediamine, N,N'-dimethylethylenediamine, N,N,N'-
trimethylethylenediamine,
N,N-dimethylpropylenediamine, N,N'-dimethylpropylenediamine, diethylene-
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triamine, triethylenetetramine, 2-(2-aminoethylamino)ethanol, 4-(3-
aminopropyl)-
morpholine, and mixtures thereof.
The Mannish reaction product of the present invention can be prepared by
reacting the alkyl-substituted hydroxyaromatic compound, aldehyde and
polyamine
by well known methods including the method described in U.S. Patent 5,876,468.
The fluidizer of the present invention comprises a polyether, a
polyetheramine, or mixtures thereof. The polyether of the present invention
can be
represented by the formula RO[CH2CH(Rl)O]XH where R is a hydrocarbyl group; Rl
is selected from the group consisting of hydrogen, alkyl groups of 1 to about
14
carbon atoms, and mixtures thereof; and x is a number from 2 to about 50. The
hydrocarbyl group R is a univalent hydrocarbon group as described above for
the
hydrocarbyl-substituted polyamine, has one or more carbon atoms, and includes
alkyl and alkylphenyl groups having about 7 to 30 total carbon atoms,
preferably
about 9 to 25 total carbon atoms, and more preferably about 11 to 20 total
carbon
atoms. The repeating oxyalkylene units are preferably derived from ethylene
oxide,
propylene oxide, and butylene oxide. The number of oxyalkylene units x is
preferably about 10 to 35, and more preferably about 18 to 27. The polyether
of the
present invention can be prepared by various well known methods including
condensing one mole of an alcohol or alkylphenol with two or more moles of an
alleylene oxide, mixture of alkylene oxides, or with several alkylene oxides
in
sequential fashion usually in the presence of a base catalyst. U.S. Patent
5,094,667
provides reaction conditions for preparing a polyether. Suitable polyethers
are
commercially available from Dow Chemicals, Huntsman, ICI and include the
Actaclear" series from Bayer.
The polyetheramine of the present invention can be represented by the
formula R[OCH2CH(Rl)]nA where R is a hydrocarbyl group as described above for
polyethers; Rl is selected from the group consisting of hydrogen, alkyl groups
of 1
to 14 carbon atoms, and mixtures thereof; n is a number from 2 to about 50;
and A is
selected from the group consisting of -OCH2CH2CH2NRZR2 and -NR3R3 where
each RZ is independently hydrogen or a hydrocarbyl group of one or more carbon
atoms, and each R3 is independently hydrogen, a hydrocarbyl group of one or
more
carbon atoms, or -[R4N(RS)]pRG where R4 is C2-Clo alkylene, RS and R6 are
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independently hydrogen or a hydrocarbyl group of one or more carbon atoms, and
p
is a number from 1 to about 7. The polyetheramine is preferably derived from
ethylene oxide, propylene oxide, or butylene oxide. The number of oxyalkylene
units n in the polyetheramine is preferably about 10 to 35, and more
preferably about
18 to 27. The polyetheramine of the present invention can be prepared by
various
well know methods. A polyether derived from an alcohol or alkylphenol as
described above can be condensed with ammonia, an amine or a polyamine in a
reductive amination to form a polyetheramine as described in European
Publication
No. EP 310875. Alternatively, the polyether can be condensed with
acrylonitrile
and the nitrile intermediate hydrogenated to form a polyetheramine as
described in
U.S. Patent 5,094,667. Polyetheramines where A is
-OCHZCHZCH2NH2 are preferred. Polyetheramines are commercially available in
the Techron~ series from Chevron and in the Jeffamine° series from
Huntsman.
The fuel composition of the present invention includes a combination of
nitrogen-containing detergents comprising a hydrocarbyl-substituted polyamine
and
a Mannich reaction product as described above which can be in a weight ratio
of the
polyamine to the Mannich reaction product of about 0.2:1 to 1:0.2 and in other
embodiments of about 0.5:1 to 1:0.5, of about 0.75:1 to 1:0.75, and of about
1:1.
Each of the nitrogen-containing detergents can be present in the fuel
composition at
about 20-100 ppm by weight, preferably at about 22-80 ppm by weight, and more
preferably at about 24-60 ppm by weight. The fuel composition optionally
includes
a fluidizer comprising a polyether, a polyetheramine, or mixtures thereof as
described above where the weight ratio of the fluidizer to the combination of
the
nitrogen-containing detergents is less than 0.5, in another embodiment less
than 0.3,
and in a further embodiment less than 0.2
In another embodiment of the present invention the fuel composition
comprises the combination of nitrogen-containing detergents, the hydrocarbyl-
substituted polyamine and Mannich reaction product, at or greater than about
60
ppm by weight as illustrated in the examples of Table 1 and 2 hereinbelow.
A method of the present invention of operating an internal combustion
engine comprises fueling the engine with the fuel composition of the present
invention which comprises the hydrocarbon fuel, the combination of nitrogen-
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containing detergents, and optionally the fluidizer as described in this
application.
In another embodiment of the present invention, a method of controlling
deposits in
an internal combustion engine comprises fueling the engine with the fuel
composition of the present invention as described in this application. The
benefits
of the methods of the present invention are illustrated in the examples of
Table 1 and
2 hereinbelow.
The fuel composition of the present invention can include a solvent to
facilitate handling and transfer of fuel additives and fuel additive
concentrates and to
provide homogeneous fuel additive concentrates and fuel compositions. The
solvent
can be an aliphatic hydrocarbon, aromatic hydrocarbon, glycol ether, alcohol,
or
mixtures thereof. Examples of suitable solvents include various naphthas,
various
kerosenes, benzene, toluene, xylenes, aliphatic alcohols having 2 to 10 carbon
atoms, or mixtures thereof.
The fuel composition of the present invention can include additional fuel
additives depending on the requirements of the engine it is used in. In
general the
fuel composition can include antioxidants such as hindered phenols,
supplemental
detergents like succinimides, corrosion inhibitors such as alkenylsuccinic
acids,
antistatic agents, biocides, demulsifiers, and additional fluidizers such as
mineral
oils and poly(alpha-olefins). Gasoline fuel compositions can contain antiknock
additives such as methylcyclopentadienyl manganese tricarbonyl, haloalkane
lead
scavengers, and anti-valve seat recession additives such as allcali metal
sulphosuccinate salts. Diesel fuel compositions can contain organo nitrite or
nitrate
cetane improvers, cold flow improvers such as copolymers of ethylene and vinyl
acetate, smoke suppressants, antifoam agents like silicone fluids, and
lubricity
agents such as tall oil fatty acids.
The fuel composition of the present invention is generally prepared by
mixing the components which can include the hydrocarbon fuel, the nitrogen-
containing detergents, fluidizer, solvent, and additional fuel additives at
ambient
temperature or at an elevated temperature of about 40 to 60°C until the
mixture is
homogeneous. The various fuel additive and solvent components can be added to
the hydrocarbon fuel separately but are usually added as a mixture or fuel
additive
concentrate which is prepared in the same way as the fuel composition.
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The patent documents cited in this application regarding methods of
preparation are incorporated herein by reference for their disclosure of these
methods of preparation.
The advantages of the present invention in controlling deposits in an internal
combustion engine are illustrated in the following examples in Table 1 and 2.
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Table 1
BMWs 2,500 Miles with Unleaded Gasoline Containing Ethanol
Example A B
HydrocarbylMannich, Fluidizer,Ratio of Intake
Valve
Polyamineb,ppm activesPpm activesFluidizer Deposits,
to ml
m actives A + B
1 61.6 - 31.6" 0.51 282
(com arative)
2 68.4 - 35.1" 0.51 85
(com arative)
3 30.2 - 46.4e 1.54 172
(com arative)
4 31.7 32.7 3.9e 0.06 48
36.0 37.1 - - 43
Table 2
5 BMWs 2,500 Miles with Unleaded Gasoline
Example A B
HydrocarbylMannich~, Polyetherd,Ratio of Intake
Valve
Polyamineb,ppm activesppm activesPolyether Deposits,
to mg
p m actives A + B
6 68.4 - 35.1 0.51 25.4
(compar
ative)
7 - 57.5 28.3 0.49 23.0
(compar
ative)
8 40.0 41.2 - - 8.6
aFuel induction system deposit test run in BMW vehicle on intake valve
deposits for
2,500 miles test cycle.
bHydrocarbyl-substituted polyamine from condensation of chlorinated 1300
molecular weight polyisobutylene and ethylenediamine.
°Mannich reaction product of a) alkylphenol from 1000 molecular weight
high
vinylidene polyisobutylene, b) formaldehyde and c) ethylenediamine.
dPolyether from one mole of Ci2-is linear alcohol condensed with 22-24 moles
of
propylene oxide.
ePolyetheramine from one mole of Cla-is linear alcohol condensed with 22-24
moles
of propylene oxide, then cyanoethylation of the propoxylated alcohol with
acrylonitrile and hydrogenation of the nitrite intermediate to form the
polyetheramine.
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