U.S. patent application number 16/041176 was filed with the patent office on 2020-01-23 for fuel-soluble synergistic cleaning mixture for high pressure gasoline engines.
The applicant listed for this patent is Afton Chemical Corporation. Invention is credited to Michel Nuckols, Charles Shanahan.
Application Number | 20200024536 16/041176 |
Document ID | / |
Family ID | 67438049 |
Filed Date | 2020-01-23 |
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United States Patent
Application |
20200024536 |
Kind Code |
A1 |
Shanahan; Charles ; et
al. |
January 23, 2020 |
Fuel-Soluble Synergistic Cleaning Mixture for High Pressure
Gasoline Engines
Abstract
The present disclosure relates to methods and fuel compositions
for reducing fuel injector deposits in gasoline engines operated at
high fuel pressures. The fuel compositions include hydrocarbons
boiling in the gasoline range and a synergistic fuel injector
cleaning mixture.
Inventors: |
Shanahan; Charles;
(Richmond, VA) ; Nuckols; Michel; (Midlothian,
VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Afton Chemical Corporation |
Richmond |
VA |
US |
|
|
Family ID: |
67438049 |
Appl. No.: |
16/041176 |
Filed: |
July 20, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 2270/023 20130101;
C10L 1/2383 20130101; F02B 2075/125 20130101; C10L 1/224 20130101;
C10L 1/232 20130101; C10L 10/04 20130101; F02B 2201/02 20130101;
C10L 2200/0259 20130101; C10L 10/18 20130101; C10L 1/22 20130101;
F02B 77/04 20130101; C10L 10/06 20130101 |
International
Class: |
C10L 10/06 20060101
C10L010/06; C10L 1/232 20060101 C10L001/232; C10L 1/224 20060101
C10L001/224; C10L 10/04 20060101 C10L010/04 |
Claims
1. A method of reducing fuel injector deposits in a gasoline
engine, the method comprising: providing a fuel composition at a
pressure of about 1,000 to about 7,500 psi to a fuel injector of a
gasoline engine and combusting the fuel composition in the gasoline
engine; the fuel composition including a major amount of gasoline
and a minor amount of a fuel injector cleaning mixture; the fuel
injector cleaning mixture including a first additive of Formula I
and a second additive of Formula II ##STR00008## wherein R and R'
are independently alkylene linkers having 1 to 10 carbon atoms;
R.sub.1 is a hydrocarbyl group or optionally substituted
hydrocarbyl group, or an aryl group or optionally stustituted aryl
group; R.sub.2 is independently a linear or branched C1 to C4 alkyl
group; R.sub.3 is hydrogen or a C1 to C4 alkyl group; R.sub.4 is a
hydrocarbyl group; R.sub.5 is hydrogen, an alkyl group, an aryl
group, --OH, --NHR.sub.6, or a polyamine and wherein R.sub.6 is a
hydrogen or an alkyl group.
2. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein a ratio of the additive of
Formula I to the additive of Formula II is about 1:8 to about
8:1.
3. The method of reducing fuel injector deposits in a gasoline
engine according to claim 2, wherein the fuel composition includes
about 1.5 to about 100 ppmw of the additive of Formula I and about
3 to about 800 ppmw of the additive of Formula II.
4. The method of reducing fuel injector deposits in a gasoline
engine according to claim 2, wherein the fuel composition includes
no more than about 600 ppmw of the fuel injector cleaning
mixture.
5. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein the fuel composition further
includes about 45 to about 1000 ppmw of a separate intake valve
deposit (IVD) control additive selected from a Mannich detergent,
polyetheramine detergent, hydrocarbyl amine detergent, and
combinations thereof.
6. The method of reducing fuel injector deposits in a gasoline
engine according to claim 5, wherein the fuel composition further
includes at least one additive selected from the group consisting
of antioxidants, carrier fluids, metal deactivators, dyes, markers,
corrosion inhibitors, biocides, antistatic additives, drag reducing
agents, demulsifiers, emulsifiers, dehazers, anti-icing additives,
antiknock additives, anti-valve-seat recession additives, lubricity
additives, surfactants and combustion improvers.
7. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein the fuel injector cleaning
mixture achieves about 30 to about 100 percent clean-up of fuel
injector deposits in the gasoline engine when supplied at pressures
of about 1,000 psi to about 7,500 psi and when the clean-up of
injector deposits is measured by at least one of long-term fuel
trim, injector pulse width, injection duration, injector flow, and
combinations thereof.
8. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein R and R' are independently
alkylene linkers having 1 to 3 carbon atoms and R.sub.1 is a C8 to
C20 hydrocarbyl group.
9. The method of reducing fuel injector deposits in a gasoline
engine according to claim 8, wherein R' includes a methylene
linker.
10. The method of reducing fuel injector deposits in a gasoline
engine according to claim 9, wherein R.sub.2 is a methyl group.
11. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein the additive of Formula II
includes a hydrocarbyl substituted succinimide derived from
ethylene diamine, diethyelene triamine, triethylene tetraamine,
tetraethylene pentamine, pentaethylene hexamine,
N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine and
combinations thereof.
12. The method of reducing fuel injector deposits in a gasoline
engine according to claim 11, wherein R.sub.4 in the compound of
Formula II is a hydrocarbyl group having a number average molecular
weight from about 450 to about 3000 and R.sub.5 is derived from
tetraethylene pentamine and derivatives thereof.
13. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein the fuel composition is
provided at a pressure of about 500 to about 4,000 psi.
14. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein R.sub.1 is oleyl derived and
wherein R.sub.5 is derived from ethylene diamine, diethyelene
triamine, triethylene tetraamine, tetraethylene pentamine,
pentaethylene hexamine,
N-N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine, and
combinations thereof.
15. The method of reducing fuel injector deposits in a gasoline
engine according to claim 1, wherein R and R' are independently
alkylene linkers having 1 to 3 carbon atoms, R.sub.1 is a C8 to C20
hydrocarbyl group, and wherein R.sub.4 in the compound of Formula
II is a hydrocarbyl group having a number average molecular weight
from about 450 to about 3000 and R.sub.5 is derived from ethylene
diamine, diethyelene triamine, triethylene tetraamine,
tetraethylene pentamine, pentaethylene hexamine, N-N'
-(iminodi-2,1,ethanediyl)bis-1,3 -propanediamine, and combinations
thereof.
16. The method of reducing fuel injector deposits in a gasoline
engine according to claim 15, wherein R' is a methylene linker.
17. The method of reducing fuel injector deposits in a gasoline
engine according to claim 15, wherein R.sub.2 is a methyl group.
Description
FIELD
[0001] The present disclosure relates to methods for reducing fuel
injector deposits in gasoline engines operating at high fuel
pressures. More particularly, the disclosure relates to methods of
cleaning up fuel injectors operating at high fuel pressures by
combusting a gasoline composition including a synergistic
combination of a fuel-soluble cleaning mixture.
BACKGROUND
[0002] Over the years considerable work has been devoted to
additives for controlling (preventing or reducing) deposit
formation in the fuel induction systems of gasoline internal
combustion engines. In particular, additives that can effectively
control fuel injector deposits, intake valve deposits, and
combustion chamber deposits represent the focal point of
considerable research activities in the field. However, prior fuel
additives are often less effective when used in newer engine
technology.
[0003] Newer engine technology, for instance, includes systems that
supply fuel at dramatically increased fuel pressure and, because of
this high fuel pressure, new engine technology presents challenges
not found in prior engine technology running at substantially lower
fuel pressures. For example, prior carbureted engines typically
operated at a fuel pressure of 4 to 15 psi and prior multi-port
fuel injected engines are designed to operate at 30 to 60 psi.
Newer engine technology, on the other hand, is being developed for
non-idle operation at greater than 500 psi fuel pressure. In view
of this difference, there are a number of technical issues to be
resolved with this new engine technology, and one of them is
injector performance and cleanliness when operated at such
dramatically higher fuel pressures.
[0004] Unfortunately, conventional fuel additives often found
effective when combusted in gasoline engines operating at lower
fuel pressures do not necessarily translate to the same performance
when combusted in gasoline engines that are operated at fuel
pressures 15 to even 100 times higher. For instance, fuel
additives, such as hydrocarbyl substituted succinimides, often used
as detergents in fuel for keeping injectors clean when operated at
low pressures, do not provide the same level of injector
performance when operated in gasoline engines at high fuel
pressures. In particular, these conventional additives are not
effective to provide clean-up performance of already fouled
injectors when the engine is operated at the high fuel pressures of
newer engine technology.
BRIEF DESCRIPTION OF THE FIGURES
[0005] FIG. 1 is a graph showing the clean-up performance of fuel
injector cleaning mixtures of the present disclosure when combusted
in a gasoline engine operated at high fuel pressures.
SUMMARY
[0006] In one approach or embodiment, a method is provided that
reduces fuel injector deposits in a high pressure gasoline engine.
The method includes injecting a fuel composition at a pressure
(such as a non-idle pressure) of about 500 to about 7,500 psi to a
gasoline engine and combusting the fuel composition in the gasoline
engine. The fuel composition includes a major amount of gasoline
and a minor amount of a fuel injector cleaning mixture. The fuel
injector cleaning mixture includes a first additive of Formula I
and a second additive of Formula II
##STR00001##
wherein R and R' are independently alkylene linkers having 1 to 10
carbon atoms (in other approaches, 1 to 3 carbon atoms); R.sub.1 is
a hydrocarbyl group or optionally substituted hydrocarbyl group, or
an aryl group or optionally substituted aryl group; R.sub.2 is
independently a linear or branched C1 to C4 alkyl group; R.sub.3 is
hydrogen or a C1 to C4 alkyl group; R.sub.4 is a hydrocarbyl group
(such as a polyisobutylene and the like as discussed more below);
R.sub.5 is hydrogen, an alkyl group, an aryl group, --OH,
--NHR.sub.6, a polyamine, or an alkyl group containing one or more
primary, secondary, or tertiary amino groups and wherein R.sub.6 is
a hydrogen or an alkyl group.
[0007] In other approaches or embodiments, the method of the
previous paragraph may also include one or more further features in
any combination selected from the following: wherein a ratio of the
additive of Formula I to the additive of Formula II is about 1:8 to
about 8:1; and/or wherein the fuel composition includes about 1.5
to about 100 ppmw of the additive of Formula I and about 3 to about
800 ppmw of the additive of Formula II; and/or wherein the fuel
composition includes no more than about 600 ppmw of the fuel
injector cleaning mixture; and/or wherein the fuel composition
further includes about 45 to about 1000 ppmw of a separate intake
valve deposit (IVD) control additive selected from a Mannich
detergent, polyetheramine detergent, hydrocarbyl amine detergent,
and combinations thereof; and/or wherein the fuel composition
further includes at least one additive selected from the group
consisting of antioxidants, carrier fluids, metal deactivators,
dyes, markers, corrosion inhibitors, biocides, antistatic
additives, drag reducing agents, demulsifiers, emulsifiers,
dehazers, anti-icing additives, antiknock additives,
anti-valve-seat recession additives, lubricity additives,
surfactants and combustion improvers; and/or wherein the fuel
injector cleaning mixture achieves about 30 to about 100 percent
clean-up of fuel injector deposits in the gasoline engine when
supplied at pressures (such as non-idle pressures) of about 500 psi
to about 7,500 psi and when the clean-up of injector deposits is
measured by at least one of long-term fuel trim, injector pulse
width, injection duration, injector flow, and combinations thereof;
and/or wherein R and R' are independently alkylene linkers having 1
to 3 carbon atoms and R.sub.1 is a C8 to C20 hydrocarbyl group;
and/or wherein R' is a methylene linker; and/or wherein R.sub.2 is
a methyl group; and/or wherein the additive of Formula II includes
a hydrocarbyl substituted succinimide derived from ethylene
diamine, diethyelene triamine, triethylene tetraamine,
tetraethylene pentamine, pentaethylene hexamine,
N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine and
combinations thereof; and/or wherein R.sub.4 in the compound of
Formula II is a hydrocarbyl group having a number average molecular
weight from about 450 to about 3000 as measured by GPC using
polystyrene as reference and R.sub.5 is derived from tetraethylene
pentamine and derivatives thereof; and/or wherein the fuel
composition is provided at a pressure of about 1,000 to about 4,000
psi; and/or wherein R.sub.1 is oleyl derived and wherein R.sub.5 is
derived from ethylene diamine, diethyelene triamine, triethylene
tetraamine, tetraethylene pentamine, pentaethylene hexamine,
N-N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine, and
combinations thereof; and/or wherein R and R' are independently
alkylene linkers having 1 to 3 carbon atoms, R.sub.1 is a C8 to C20
hydrocarbyl group, and wherein R.sub.4 in the compound of Formula
II is a hydrocarbyl group having a number average molecular weight
from about 450 to about 3000 as measured by GCP using polystyrene
as a reference and R.sub.5 is derived from ethylene diamine,
diethyelene triamine, triethylene tetraamine, tetraethylene
pentamine, pentaethylene hexamine,
N-N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine, and
combinations thereof; and/or wherein R' includes a methylene
linker; and/or wherein R.sub.2 is a methyl group.
DETAILED DESCRIPTION
[0008] The present disclosure describes methods of reducing
deposits on fuel injectors in a gasoline engine operated at high
fuel pressures using a fuel soluble cleaning mixture. In one
approach or embodiment, the fuel soluble cleaning mixture includes
a synergistic combination of a first cleaning additive of a
quaternary ammonium internal salt combined with a second cleaning
additive of a hydrocarbyl substituted dicarboxylic anhydride
derivative. Low treat rates of this synergistic combination of
cleaning additives reduce fuel injector deposits and/or clean-up
fouled fuel injectors in a gasoline engine when that engine is
operated at high fuel pressures (such as non-idle fuel pressures)
greater than about 500 psi (in some approaches, about 500 to about
7,500 psi), and in yet further approaches greater than about 1,000
psi (in other approaches, about 1,000 to about 7,500 psi). It was
unexpectedly discovered that the combination of the two cleaning
additives together enables a substantially greater level of
injector clean-up performance (and in some approaches at lower
treat rates) than either cleaning additive can achieve individually
when used in a gasoline fuel at such high fuel pressures.
[0009] The First Cleaning Additive: The first cleaning additive of
the synergistic mixture, in one approach, is a quaternary ammonium
internal salt obtained from amines or polyamines that is
substantially devoid of any free anion species. For example, such
additive may be made by reacting a tertiary amine of Formula
III
##STR00002##
wherein each of R.sub.9, R.sub.10, and R.sub.11 is selected from
hydrocarbyl groups containing from 1 to 200 carbon atoms, with a
halogen substituted C2-C8 carboxylic acid, ester, amide, or salt
thereof. What is generally to be avoided in the reaction is
quaternizing agents selected from the group consisting of
hydrocarbyl substituted carboxylates, carbonates,
cyclic-carbonates, phenates, epoxides, or mixtures thereof. In one
embodiment, the halogen substituted C2-C8 carboxylic acid, ester,
amide, or salt thereof may be selected from chloro-, bromo-,
fluoro-, and iodo-C2-C8 carboxylic acids, esters, amides, and salts
thereof. The salts may be alkali or alkaline earth metal salts
selected from sodium, potassium, lithium calcium, and magnesium
salts. A particularly useful halogen substituted compound for use
in the reaction is the sodium or potassium salt of a chloroacetic
acid.
[0010] As used herein the term "substantially devoid of free anion
species" means that the anions, for the most part are covalently
bound to the product such that the reaction product as made does
not contain any substantial amounts of free anions or anions that
are ionically bound to the product. In one embodiment,
"substantially devoid" means from 0 to less than about 2 wt. % of
free anion species.
[0011] In another approach or embodiment, a tertiary amine
including monoamines and polyamines may be reacted with the halogen
substituted acetic acid or derivative thereof to provide the first
detergent additive of the synergistic mixture. Suitable tertiary
amine compounds are those of Formula IV
##STR00003##
wherein each of R.sub.9, R.sub.10, and R.sub.11 is selected, as
noted above, from hydrocarbyl groups containing from 1 to 200
carbon atoms. Each hydrocarbyl group R.sub.9 to Ru may
independently be linear, branched, substituted, cyclic, saturated,
unsaturated, or contain one or more hetero atoms. Suitable
hydrocarbyl groups may include, but are not limited to alkyl
groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy
groups, aryloxy groups, amido groups, ester groups, imido groups,
and the like. Any of the foregoing hydrocarbyl groups may also
contain hetero atoms, such as oxygen or nitrogen atoms.
Particularly suitable hydrocarbyl groups may be linear or branched
alkyl groups. Some representative examples of amine reactants which
can be reacted to yield compounds of this disclosure include, but
are not limited to, trimethyl amine, triethyl amine, tri-n-propyl
amine, dimethylethyl amine, dimethyl lauryl amine, dimethyl oleyl
amine, dimethyl stearyl amine, dimethyl eicosyl amine, dimethyl
octadecyl amine, N-methyl piperidine, N,N'-dimethyl piperazine,
N-methyl-N-ethyl piperazine, N-methyl morpholine, N-ethyl
morpholine, N-hydroxyethyl morpholine, pyridine, triethanol amine,
triisopropanol amine, methyl diethanol amine, dimethyl ethanol
amine, lauryl diisopropanol amine, stearyl diethanol amine, dioleyl
ethanol amine, dimethyl isobutanol amine, methyl diisooctanol
amine, dimethyl propenyl amine, dimethyl butenyl amine, dimethyl
octenyl amine, ethyl didodecenyl amine, dibutyl eicosenyl amine,
triethylene diamine, hexa-methylenetetramine,
N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethyl-propylenediamine,
N,N,N',N'-tetraethyl-1,3-propanediamine, methyldi-cyclohexyl amine,
2,6-dimethylpyridine, dimethylcylohexylamine, C10-C30-alkyl or
alkenyl-substituted amidopropyldimethylamine, C12-C200-alkyl or
alkenyl-substituted succinic-carbonyl-dimethylamine, and the like.
A suitable first cleaning additive may be the internal salts of
oleyl amidopropyl dimethylamino or oleyl dimethyl amine.
[0012] If the amine contains solely primary or secondary amino
groups, it may be necessary to alkylate at least one of the primary
or secondary amino groups to a tertiary amino group prior to the
reaction with the halogen substituted C2-C8 carboxylic acid, ester,
amide, or salt thereof. In one embodiment, alkylation of primary
amines and secondary amines or mixtures with tertiary amines may be
exhaustively or partially alkylated to a tertiary amine. It may
also be necessary to properly account for the hydrogens on the
nitrogen and provide base or acid as required (e.g., alkylation up
to the tertiary amine requires removal (neutralization) of the
hydrogen (proton) from the product of the alkylation). If
alkylating agents, such as, alkyl halides or dialkyl sulfates are
used, the product of alkylation of a primary or secondary amine is
a protonated salt and needs a source of base to free the amine for
further reaction.
[0013] The halogen substituted C2-C8 carboxylic acid, ester, amide,
or salt thereof for use in making the first cleaning additive may
be derived from a mono-, di-, or tri- chloro- bromo-, fluoro-, or
iodo-carboxylic acid, ester, amide, or salt thereof selected from
the group consisting of halogen-substituted acetic acid, propanoic
acid, butanoic acid, isopropanoic acid, isobutanoic acid,
tert-butanoic acid, pentanoic acid, heptanoic acid, octanoic acid,
halo-methyl benzoic acid, and isomers, esters, amides, and salts
thereof The salts of the carboxylic acids may include the alkali or
alkaline earth metal salts, or ammonium salts including, but not
limited to the Na, Li, K, Ca, Mg, triethyl ammonium and triethanol
ammonium salts of the halogen-substituted carboxylic acids. A
particularly suitable halogen substituted carboxylic acid, or salt
thereof may be selected from chloroacetic acid and sodium or
potassium chloroacetate. The amount of halogen substituted C2-C8
carboxylic acid, ester, amide, or salt thereof relative to the
amount of tertiary amine reactant may range from a molar ratio of
about 1:0.1 to about 0.1:1.0.
[0014] The internal salts made according to the foregoing procedure
may include, but are not limited to (1) hydrocarbyl substituted
compounds of the formula R''--NMe.sub.2CH.sub.2COO where R'' is
from C1 to C30 or a substituted amido group; (2) fatty amide
substituted internal salts; and (3) hydrocarbyl substituted imide,
amide, or ester internal salts wherein the hydrocarbyl group has 8
to 40 carbon atoms. Particularly suitable internal salts may be
selected from the group consisting of polyisobutenyl substituted
succinimide, succinic diamide, and succinic diester internal salts;
C8-C40 alkenyl substituted succinimide, succinic diamide, and
succinic diester internal salts; oleyl amidopropyl dimethylamino
internal salts; and oleyl dimethylamino internal salts.
[0015] In yet another approach or embodiment, the first fuel
injector cleaning additive of the synergistic mixture may be a
quaternary ammonium internal salt of Formula I
##STR00004##
wherein R and R' are independently alkylene linkers having 1 to 10
carbon atoms (in other approaches 1 to 3 carbon atoms); R.sub.1 is
independently a hydrocarbyl group or optionally substituted
hydrocarbyl group, or an aryl group or optionally substituted aryl
group; R.sub.2 is independently a linear or branched C1 to C4 alkyl
group; R.sub.3 is a hydrogen atom or a C1 to C4 alkyl group. The
internal salts of Formula I may also be substantially devoid of
free anion species as discussed above.
[0016] In another approach, the first fuel injector cleaning
additive includes the compound of Formula I above wherein R is a
propylene linker, R is a methylene linker, R.sub.1 is a C8 to C20
hydrocarbyl group, and R.sub.2 is a methyl group. In yet other
approaches, the first fuel injector cleaning additive is selected
from oleyl amidopropyl dimethylamine internal salts or oleyl
dimethylamino internal salts. In some approaches, such fuel
injector cleaning additives may be substantially devoid of free
anion species.
[0017] While the first fuel injector cleaning additive may provide
limited reduction of fuel injector deposits and/or clean-up
performance of injector deposits in engines operating at high
pressures by itself, as discussed more below, it was unexpectedly
discovered that when the first fuel injector cleaning additive is
combined with other fuel injector cleaning additives, a
dramatically improved clean-up performance of engines is achieved
when those engines are operated at high pressure.
[0018] The Second Cleaning Additive: The second cleaning additive
of the synergistic mixture, in one approach, is a hydrocarbyl
substituted dicarboxylic anhydride derivative. In some approaches,
the second cleaning additive includes hydrocarbyl succinimides,
succinamides, succinimide-amides and succinimide-esters. These
nitrogen-containing derivatives of hydrocarbyl succinic acylating
agents may be prepared by reacting a hydrocarbyl-substituted
succinic acylating agent with an amine, polyamine, or alkyl amine
having one or more primary, secondary, or tertiary amino
groups.
[0019] In one approach or embodiment, the hydrocarbyl substituted
dicarboxylic anhydride derivative may include a hydrocarbyl
substituent having a number average molecular weight ranging from
about 450 to about 3000 as measured by GPC using polystyrene as
reference. The derivative may be selected from a diamide,
acid/amide, acid/ester, diacid, amide/ester, diester, and imide.
Such derivative may be made from reacting a hydrocarbyl substituted
dicarboxylic anhydride with ammonia, a polyamine, or an alkyl amine
having one or more primary, secondary, or tertiary amino groups. In
some embodiments, the polyamine or alkyl amine may be tetraethylene
pentamine (TEPA), triethylenetetramine (TETA), and the like amines.
In other approaches, the polyamine or alkyl amine may have the
formula H.sub.2N--((CHR.sub.12--(CH.sub.2).sub.q--NH).sub.r--H,
wherein R.sub.12 is hydrogen or an alkyl group having from 1 to 4
carbon atoms, q is an integer of from 1 to 4 and r is an integer of
from 1 to 6, and mixtures thereof. In other approaches, a molar
ratio of the hydrocarbyl substituted dicarboxylic anhydride reacted
with the ammonia, polyamine, or alkyl amine may be from about 0.5:1
to about 2:1, in other approaches about 1:1 to about 2:1.
[0020] In other approaches, the hydrocarbyl substituted
dicarboxylic anhydride may be a hydrocarbyl carbonyl compound of
the Formula V
##STR00005##
wherein R.sub.13 is a hydrocarbyl group derived from a polyolefin.
In some aspects, the hydrocarbyl carbonyl compound may be a
polyalkylene succinic anhydride reactant wherein R.sub.13 is a
hydrocarbyl moiety, such as for example, a polyalkenyl radical
having a number average molecular weight of from about 450 to about
3000 as measured by GPC using polystyrene as reference. For
example, the number average molecular weight of R.sub.13 may range
from about 600 to about 2500, or from about 700 to about 1500, as
measured by GPC using polystyrene as reference. A particularly
useful R.sub.13 has a number average molecular weight of about 950
to about 1000 Daltons (as measured by GPC using polystyrene as
reference) and comprises polyisobutylene. Unless indicated
otherwise, molecular weights in the present specification are
number average molecular weights as measured by GPC using
polystyrene as reference.
[0021] The R.sub.13 hydrocarbyl moiety may include one or more
polymer units chosen from linear or branched alkenyl units. In some
aspects, the alkenyl units may have from about 2 to about 10 carbon
atoms. For example, the polyalkenyl radical may comprise one or
more linear or branched polymer units chosen from ethylene
radicals, propylene radicals, butylene radicals, pentene radicals,
hexene radicals, octene radicals and decene radicals. In some
aspects, the R.sub.13 polyalkenyl radical may be in the form of,
for example, a homopolymer, copolymer or terpolymer. In one aspect,
the polyalkenyl radical is isobutylene. For example, the
polyalkenyl radical may be a homopolymer of polyisobutylene
comprising from about 10 to about 60 isobutylene groups, such as
from about 20 to about 30 isobutylene groups. The polyalkenyl
compounds used to form the R.sub.13 polyalkenyl radicals may be
formed by any suitable methods, such as by conventional catalytic
oligomerization of alkenes.
[0022] In some aspects, high reactivity polyisobutenes having
relatively high proportions of polymer molecules with a terminal
vinylidene group may be used to form the R.sub.13 group. In one
example, at least about 60%, such as about 70% to about 90%, of the
polyisobutenes comprise terminal olefinic double bonds. High
reactivity polyisobutenes are disclosed, for example, in U.S. Pat.
No. 4,152,499, the disclosure of which is herein incorporated by
reference in its entirety.
[0023] In some aspects, approximately one mole of maleic anhydride
may be reacted per mole of polyalkylene, such that the resulting
polyalkenyl succinic anhydride has about 0.8 to about 1 succinic
anhydride group per polyalkylene substituent. In other aspects, the
molar ratio of succinic anhydride groups to polyalkylene groups may
range from about 0.5 to about 3.5, such as from about 1 to about
1.1.
[0024] The hydrocarbyl carbonyl compounds may be made using any
suitable method. One example of a method for forming a hydrocarbyl
carbonyl compound comprises blending a polyolefin and maleic
anhydride. The polyolefin and maleic anhydride reactants are heated
to temperatures of, for example, about 150.degree. C. to about
250.degree. C., optionally, with the use of a catalyst, such as
chlorine or peroxide. Another exemplary method of making the
polyalkylene succinic anhydrides is described in U.S. Pat. No.
4,234,435, which is incorporated herein by reference in its
entirety.
[0025] In the hydrocarbyl substituted dicarboxylic anhydride
derivative, the polyamine reactant may be an alkylene polyamine.
For example, the polyamine may be selected from ethylene polyamine,
propylene polyamine, butylenes polyamines, and the like. In one
approach, the polyamine is an ethylene polyamine that may be
selected from ethylene diamine, diethylene triamine, triethylene
tetramine, tetraethylene pentamine, pentaethylene hexamine, and
N,N'-(iminodi-2,1,ethanediyl) bis-1,3-propanediamine. A
particularly useful ethylene polyamine is a compound of the formula
H.sub.2N--((CHR.sub.12--(CH.sub.2).sub.q--NH).sub.r--H, wherein
R.sub.12 is hydrogen, q is 1 and r is 4.
[0026] In yet further approaches, the second fuel injector cleaning
additive of the synergistic mixture is a compound of Formula II
##STR00006##
wherein R.sub.4 is a hydrocarbyl group (such as polyisobutylene
and/or the other above described R.sub.13 moieties) and R.sub.5 is
a hydrogen, an alkyl group, an aryl group, --OH, --NHR.sub.6, or a
polyamine, or an alkyl group containing one or more primary,
secondary, or tertiary amino groups. In some approaches, R.sub.5 is
derived from ethylene diamine, diethyelene triamine, triethylene
tetraamine, tetraethylene pentamine, pentaethylene hexamine,
N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine and
combinations thereof. In yet other approaches R.sub.5 is a compound
of Formula VI
##STR00007##
wherein A is NR.sub.6 or an oxygen atom, R.sub.6, R.sub.7, and
R.sub.8 are independently a hydrogen atom or an alkyl group, m and
p are integers from 2 to 8; and n is an integer from 0 to 4. In
some approaches, R.sub.7 and R.sub.8 of Formula VI, together with
the nitrogen atom to which they are attached, form a 5 membered
ring.
[0027] Synergistic Cleaning Mixture: The above-described fuel
soluble synergistic cleaning mixture of the first cleaning additive
and the second cleaning additive are effective to reduce deposits
on fuel injectors and, in particular, clean-up already fouled fuel
injectors in gasoline engines operated at fuel pressures, such as
non-idle fuel pressures, greater than 500 psi and, in other
approaches, from about 500 to about 7,500 psi (in yet further
approaches, greater than about 1,000 psi and/or from about 1,000
psi to about 7,500 psi). By clean-up, it is meant the reduction or
elimination of existing fuel injector deposits in a gasoline engine
when operated at such high pressures. For example, the synergistic
detergent mixture is preferably added to the fuel in proportions
effective to reduce the amount of injector deposits in a gasoline
engine operated on the fuel at about 500 to about 7,500 psi
containing the synergistic cleaning mixture to below the amount of
injector deposits in the same engine operated in the same manner on
the same fuel except that it is devoid of the new synergetic
cleaning mixture. Economically, it is desirable to use the least
amount of additive effective for the desired purpose. One advantage
of the synergistic cleaning mixture herein is that such mixture
achieves in some instances injector clean-up at low treat rates,
which in some approaches further enables the addition of other
additives to the fuel as described more below.
[0028] In other approaches or embodiments, the fuel-soluble
synergistic detergent mixture as described in the previous
paragraphs is added to the gasoline fuel in amounts up to about
1,000 ppmw of the fuel-soluble synergistic detergent mixture (in
other approaches up to about 600 ppmw, in yet other approaches, up
to about 400 ppmw, up to about 100 ppmw, up to about 50 ppmw, up to
about 15 ppmw, and/or up to about 12 ppmw) having a ratio of the
first cleaning additive to the second cleaning additive of about
1:8 to about 8:1. In other approaches, the fuel-soluble synergistic
detergent mixture is provided to the fuel in amounts of about 4
ppmw to about 600 ppmw, in other approaches, about 10 to about 250
ppm, in yet further approaches, about 15 to about 100 ppmw, and in
yet even further approaches about 12 to about 20 ppmw (wherein the
synergistic mixture includes both the first and second cleaning
additives combined).
[0029] In other approaches, the fuel composition includes about 1.5
to about 100 ppmw of the first cleaning additive described herein
(in other approaches, about 1.5 to about 60 ppmw), in yet further
approaches, about 1.5 to about 20 ppmw, about 15 to about 10 ppmw,
about 1.5 to about 5 ppmw) and about 3 to about 800 ppmw of the
second cleaning additive described herein (in other approaches,
about 3 to about 400 ppmw, in yet other approaches, about 3 to 100
ppmw, about 3 to about 50 ppmw, about 3 to about 20 ppmw, and/or
about 3 to about 1 ppmw, or about 7 to about 20 ppmw) where the
ratio of the first to the second cleaning additive remains about
1:8 to about 8:1 and in other approaches, about 1:2 to about 2:1,
and in yet other approaches about 1:2.
[0030] When combusting the gasoline fuel having the fuel-soluble
synergistic cleaning mixtures within an engine operating at fuel
pressures of about 500 to about 7,500 psi, the fuel-soluble
synergistic cleaning mixtures herein (as previously described in
all prior paragraphs) surprisingly achieve about 30 to about 100
percent clean-up of exiting fuel injector deposits when clean-up is
measured by long-term fuel trim (LTFT), injector pulse width,
injection duration, and/or injector flow to suggest but a few
methods of measuring injector cleanliness. In one approach, fuel
injector deposit clean-up is measured per SAE 2013-01-2626 and/or
SAE 2017-01-2298 as further discussed below. Both of these papers
are incorporated herein by reference in their entirety.
[0031] Hydrocarbon Fuel: The base fuels used in formulating the
fuel compositions of the present disclosure include any base fuels
suitable for use in the operation of gasoline engines configured to
combust fuel at the high fuel pressures discussed herein. Suitable
fuels include leaded or unleaded motor gasolines, and so-called
reformulated gasolines which typically contain both hydrocarbons of
the gasoline boiling range and fuel-soluble oxygenated blending
agents ("oxygenates"), such as alcohols, ethers and other suitable
oxygen-containing organic compounds. Preferably, the fuel is a
mixture of hydrocarbons boiling in the gasoline boiling range. This
fuel may consist of straight chain or branch chain paraffins,
cycloparaffins, olefins, aromatic hydrocarbons or any mixture of
these. The gasoline can be derived from straight run naptha,
polymer gasoline, natural gasoline or from catalytically reformed
stocks boiling in the range from about 80.degree. to about
450.degree. F. The octane level of the gasoline is not critical and
any conventional gasoline may be employed in the practice of this
invention.
[0032] Oxygenates suitable for use in the present disclosure
include methanol, ethanol, isopropanol, t-butanol, mixed C1 to C5
alcohols, methyl tertiary butyl ether, tertiary amyl methyl ether,
ethyl tertiary butyl ether and mixed ethers. Oxygenates, when used,
will normally be present in the base fuel in an amount below about
30% by volume, and preferably in an amount that provides an oxygen
content in the overall fuel in the range of about 0.5 to about 5
percent by volume.
[0033] High pressure gasoline engines are engines known to those of
ordinary skill that are configured to operate at non-idle gasoline
fuel pressures greater than about 500 psi or greater than 1,000 psi
and preferably at about 500 to about 7,500 psi (in other
approaches, about 1,000 to about 7,500 psi, about 500 to about
4,000 psi, about 1,000 to about 4,000 psi, and in yet further
approaches, about 500 to about 3,000 psi, or about 1,000 to about
3,000 psi). The hydrocarbon fuel boiling in the gasoline range may
be spark-ignited or compression ignited at such high pressures.
Such engines may include individual fuel injectors for each
cylinder or combustion chamber of the engine. Suitable gasoline
engines may include one or more high pressure pumps and suitable
high pressure injectors configured to spray fuel into each cylinder
or combustion chamber of the engine at the high pressures. In other
approaches, the engines may be operated at temperatures effective
to combust the gasoline under high compression and high pressure.
Such engines are described, for example, in US patent references US
8,235,024; US 8,701,626; US 9,638,146; US 20070250256; and/or US
20060272616 to suggest a few examples. In some instances, the
gasoline engine may also be configured to operate at an
air-to-gasoline weight ratio of about 40:1 or higher in the
combustion chamber (in some approaches, about 40:1 to about 70:1
air-to-gasoline weight ratio) to deliver fuel at the high pressures
noted herein.
[0034] Supplemental Fuel Additives: The fuel compositions of the
present disclosure may also contain supplemental additives in
addition to the fuel-soluble synergistic detergent mixture
described above. For example, supplemental additives may include
other dispersants/detergents, antioxidants, carrier fluids, metal
deactivators, dyes, markers, corrosion inhibitors, biocides,
antistatic additives, drag reducing agents, demulsifiers,
emulsifiers, dehazers, anti-icing additives, antiknock additives,
anti-valve-seat recession additives, lubricity additives,
surfactants, combustion improvers, and mixtures thereof.
[0035] One particular additional additive may be a Mannich base
detergent such as a separate intake valve deposit (IVD) control
additive including a Mannich base detergent. Suitable Mannich base
detergents for use in the fuel compositions herein include the
reaction products of a high molecular weight alkyl-substituted
hydroxyaromatic compound, aldehydes and amines. If used, the fuel
composition may include about 45 to about 1000 ppm of a Mannich
base detergent as a separate IVD control additive.
[0036] In one approach, the high molecular weight alkyl
substituents on the benzene ring of the hydroxyaromatic compound
may be derived from a polyolefin having a number average molecular
weight (Mn) from about 500 to about 3000, preferably from about 700
to about 2100, as determined by gel permeation chromatography (GPC)
using polystyrene as reference. The polyolefin may also have a
polydispersity (weight average molecular weight/number average
molecular weight) of about 1 to about 4 (in other instances, about
1 to about 2) as determined by GPC using polystyrene as
reference.
[0037] The alkylation of the hydroxyaromatic compound is typically
performed in the presence of an alkylating catalyst at a
temperature in the range of about 0 to about 200.degree. C.,
preferably 0 to 100.degree. C. Acidic catalysts are generally used
to promote Friedel-Crafts alkylation. Typical catalysts used in
commercial production include sulphuric acid, BF.sub.3, aluminum
phenoxide, methanesulphonic acid, cationic exchange resin, acidic
clays and modified zeolites.
[0038] Polyolefins suitable for forming the high molecular weight
alkyl-substituted hydroxyaromatic compounds include polypropylene,
polybutenes, polyisobutylene, copolymers of butylene and/or
butylene and propylene, copolymers of butylene and/or isobutylene
and/or propylene, and one or more mono-olefinic comonomers
copolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene,
1-octene, 1-decene, etc.) where the copolymer molecule contains at
least 50% by weight, of butylene and/or isobutylene and/or
propylene units. The comonomers polymerized with propylene or such
butenes may be aliphatic and can also contain non-aliphatic groups,
e.g., styrene, o-methylstyrene, p-methylstyrene, divinyl benzene
and the like. Thus in any case the resulting polymers and
copolymers used in forming the high molecular weight
alkyl-substituted hydroxyaromatic compounds are substantially
aliphatic hydrocarbon polymers.
[0039] Polybutylene is preferred. Unless otherwise specified
herein, the term "polybutylene" is used in a generic sense to
include polymers made from "pure" or "substantially pure" 1-butene
or isobutene, and polymers made from mixtures of two or all three
of 1-butene, 2-butene and isobutene. Commercial grades of such
polymers may also contain insignificant amounts of other olefins.
So-called high reactivity polyisobutenes having relatively high
proportions of polymer molecules having a terminal vinylidene group
are also suitable for use in forming the long chain alkylated
phenol reactant. Suitable high-reactivity polyisobutenes include
those polyisobutenes that comprise at least about 20% of the more
reactive methylvinylidene isomer, preferably at least 50% and more
preferably at least 70%. Suitable polyisobutenes include those
prepared using BF.sub.3 catalysts. The preparation of such
polyisobutenes in which the methylvinylidene isomer comprises a
high percentage of the total composition is described in U.S. Pat.
Nos. 4,152,499 and 4,605,808, which are both incorporated herein by
reference.
[0040] The Mannich detergent may be made from a high molecular
weight alkylphenol or alkylcresol. However, other phenolic
compounds may be used including high molecular weight
alkyl-substituted derivatives of resorcinol, hydroquinone,
catechol, hydroxydiphenyl, benzylphenol, phenethylphenol, naphthol,
tolylnaphthol, among others. Preferred for the preparation of the
Mannich detergents are the polyalkylphenol and polyalkylcresol
reactants, e.g., polypropylphenol, polybutylphenol,
polypropylcresol and polybutylcresol, wherein the alkyl group has a
number average molecular weight of about 500 to about 2100 as
measured by GPC using polystyrene as reference, while the most
preferred alkyl group is a polybutyl group derived from
polyisobutylene having a number average molecular weight in the
range of about 700 to about 1300 as measured by GPC using
polystyrene as reference.
[0041] The preferred configuration of the high molecular weight
alkyl-substituted hydroxyaromatic compound is that of a
para-substituted mono-alkylphenol or a para-substituted mono-alkyl
ortho-cresol. However, any hydroxyaromatic compound readily
reactive in the Mannich condensation reaction may be employed.
Thus, Mannich products made from hydroxyaromatic compounds having
only one ring alkyl substituent, or two or more ring alkyl
substituents are suitable for use in this invention. The long chain
alkyl substituents may contain some residual unsaturation, but in
general, are substantially saturated alkyl groups.
[0042] Representative amine reactants include, but are not limited
to, alkylene polyamines having at least one suitably reactive
primary or secondary amino group in the molecule. Other
substituents such as hydroxyl, cyano, amido, etc., can be present
in the polyamine. In a preferred embodiment, the alkylene polyamine
is a polyethylene polyamine. Suitable alkylene polyamine reactants
include ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine and mixtures of such amines having nitrogen
contents corresponding to alkylene polyamines of the formula
H.sub.2N-(A-NH--).sub.nH, where A in this formula is divalent
ethylene or propylene and n is an integer of from 1 to 10,
preferably 1 to 4. The alkylene polyamines may be obtained by the
reaction of ammonia and dihalo alkanes, such as dichloro
alkanes.
[0043] The amine may also be an aliphatic diamine having one
primary or secondary amino group and at least one tertiary amino
group in the molecule. Examples of suitable polyamines include
N,N,N'',N''-tetraalkyldialkylenetriamines (two terminal tertiary
amino groups and one central secondary amino group),
N,N,N',N''-tetraalkyltrialkylenetetramines (one terminal tertiary
amino group, two internal tertiary amino groups and one terminal
primary amino group),
N,N,N',N'',N''-pentaalkyltrialkylenetetramines (one terminal
tertiary amino group, two internal tertiary amino groups and one
terminal secondary amino group), N,N-dihydroxyalkyl-alpha-,
omega-alkylenediamines (one terminal tertiary amino group and one
terminal primary amino group), N,N,N'-trihydroxyalkyl-alpha,
omega-alkylenediamines (one terminal tertiary amino group and one
terminal secondary amino group),
tris(dialkylaminoalkyl)aminoalkylmethanes (three terminal tertiary
amino groups and one terminal primary amino group), and similar
compounds, wherein the alkyl groups are the same or different and
typically contain no more than about 12 carbon atoms each, and
which preferably contain from 1 to 4 carbon atoms each. Most
preferably these alkyl groups are methyl and/or ethyl groups.
Preferred polyamine reactants are N,N-dialkyl-alpha,
omega-alkylenediamine, such as those having from 3 to about 6
carbon atoms in the alkylene group and from 1 to about 12 carbon
atoms in each of the alkyl groups, which most preferably are the
same but which can be different. Most preferred is
N,N-dimethyl-1,3-propanediamine and N-methyl piperazine.
[0044] Examples of polyamines having one reactive primary or
secondary amino group that can participate in the Mannich
condensation reaction, and at least one sterically hindered amino
group that cannot participate directly in the Mannich condensation
reaction to any appreciable extent include
N-(tert-butyl)-1,3-propanediamine, N-neopentyl-1,3-propanediamine-,
N-(tert-butyl)-1-methyl-1,2-ethanediamine,
N-(tert-butyl)-1-methyl-1,3-propanediamine, and
3,5-di(tert-butyl)aminoethylpiperazine.
[0045] Representative aldehydes for use in the preparation of the
Mannich base products include the aliphatic aldehydes such as
formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde. Aromatic
aldehydes which may be used include benzaldehyde and
salicylaldehyde. Illustrative heterocyclic aldehydes for use herein
are furfural and thiophene aldehyde, etc. Also useful are
formaldehyde-producing reagents such as paraformaldehyde, or
aqueous formaldehyde solutions such as formalin. Most preferred is
formaldehyde or formalin.
[0046] The condensation reaction among the alkylphenol, the
specified amine(s) and the aldehyde may be conducted at a
temperature typically in the range of about 40.degree. C. to about
200.degree. C. The reaction can be conducted in bulk (no diluent or
solvent) or in a solvent or diluent. Water is evolved and can be
removed by azeotropic distillation during the course of the
reaction. Typically, the Mannich reaction products are formed by
reacting the alkyl-substituted hydroxyaromatic compound, the amine
and aldehyde in the molar ratio of 1.0:0.5-2.0:1.0-3.0,
respectively.
[0047] Suitable Mannich base detergents include those detergents
taught in U.S. Pat. Nos. 4,231,759; 5,514,190; 5,634,951;
5,697,988; 5,725,612; and 5,876,468, the disclosures of which are
incorporated herein by reference.
[0048] Another suitable additional fuel additive may be a
hydrocarbyl amine detergents. If used, the fuel composition may
include about 45 to about 1000 ppm of the hydrocarbyl amine
detergent. One common process involves halogenation of a long chain
aliphatic hydrocarbon such as a polymer of ethylene, propylene,
butylene, isobutene, or copolymers such as ethylene and propylene,
butylene and isobutylene, and the like, followed by reaction of the
resultant halogenated hydrocarbon with a polyamine. If desired, at
least some of the product can be converted into an amine salt by
treatment with an appropriate quantity of an acid. The products
formed by the halogenation route often contain a small amount of
residual halogen such as chlorine. Another way of producing
suitable aliphatic polyamines involves controlled oxidation (e.g.,
with air or a peroxide) of a polyolefin such as polyisobutene
followed by reaction of the oxidized polyolefin with a polyamine.
For synthesis details for preparing such aliphatic polyamine
detergent/dispersants, see for example U.S. Pat. Nos. 3,438,757;
3,454,555; 3,485,601; 3,565,804; 3,573,010; 3,574,576; 3,671,511;
3,746,520; 3,756,793; 3,844,958; 3,852,258; 3,864,098; 3,876,704;
3,884,647; 3,898,056; 3,950,426; 3,960,515; 4,022,589; 4,039,300;
4,128,403; 4,166,726; 4,168,242; 5,034,471; 5,086,115; 5,112,364;
and 5,124,484; and published European Patent Application 384,086.
The disclosures of each of the foregoing documents are incorporated
herein by reference. The long chain substituent(s) of the
hydrocarbyl amine detergent most preferably contain(s) an average
of 40 to 350 carbon atoms in the form of alkyl or alkenyl groups
(with or without a small residual amount of halogen substitution).
Alkenyl substituents derived from poly-alpha-olefin homopolymers or
copolymers of appropriate molecular weight (e.g., propene
homopolymers, butene homopolymers, C3 and C4 alpha-olefin
copolymers, and the like) are suitable. Most preferably, the
substituent is a polyisobutenyl group formed from polyisobutene
having a number average molecular weight (as determined by gel
permeation chromatography) in the range of 500 to 2000, preferably
600 to 1800, most preferably 700 to 1600.
[0049] Polyetheramines are yet another suitable additional
detergent chemistry used in the methods of the present disclosure.
If used, the fuel composition may include about 45 to about 1000
ppm of the polyetheramine detergents. The polyether backbone in
such detergents can be based on propylene oxide, ethylene oxide,
butylene oxide, or mixtures of these. The most preferred are
propylene oxide or butylene oxide or mixture thereof to impart good
fuel solubility. The polyetheramines can be monoamines, diamines or
triamines. Examples of commercially available polyetheramines are
those under the tradename JeffaminesTM available from Huntsman
Chemical company and the poly(oxyalkylene)carbamates available from
Chevron Chemical Company. The molecular weight of the
polyetheramines will typically range from 500 to 3000. Other
suitable polyetheramines are those compounds taught in U.S. Pat.
Nos. 4,191,537; 4,236,020; 4,288,612; 5,089,029; 5,112,364;
5,322,529; 5,514,190 and 5,522,906.
[0050] In some approaches, the fuel-soluble synergistic detergent
mixture may also be used with a liquid carrier or induction aid.
Such carriers can be of various types, such as for example liquid
poly-.alpha.-olefin oligomers, mineral oils, liquid
poly(oxyalkylene) compounds, liquid alcohols or polyols,
polyalkenes, liquid esters, and similar liquid carriers. Mixtures
of two or more such carriers can be employed.
[0051] Exemplary liquid carriers may include a mineral oil or a
blend of mineral oils that have a viscosity index of less than
about 120; one or more poly-.alpha.-olefin oligomers; one or more
poly(oxyalkylene) compounds having an average molecular weight in
the range of about 500 to about 3000; polyalkenes;
polyalkyl-substituted hydroxyaromatic compounds; or mixtures
thereof The mineral oil carrier fluids that can be used include
paraffinic, naphthenic and asphaltic oils, and can be derived from
various petroleum crude oils and processed in any suitable manner.
For example, the mineral oils may be solvent extracted or
hydrotreated oils. Reclaimed mineral oils can also be used.
Hydrotreated oils are the most preferred. Preferably the mineral
oil used has a viscosity at 40.degree. C. of less than about 1600
SUS, and more preferably between about 300 and 1500 SUS at
40.degree. C. Paraffinic mineral oils most preferably have
viscosities at 40.degree. C. in the range of about 475 SUS to about
700 SUS. In some instances, the mineral oil may have a viscosity
index of less than about 100, in other instances, less than about
70 and, in yet further instances, in the range of from about 30 to
about 60.
[0052] The poly-.alpha.-olefins (PAO) suitable for use as carrier
fluids are the hydrotreated and unhydrotreated poly-.alpha.-olefin
oligomers, such as, hydrogenated or unhydrogenated products,
primarily trimers, tetramers and pentamers of alpha-olefin
monomers, which monomers contain from 6 to 12, generally 8 to 12
and most preferably about 10 carbon atoms. Their synthesis is
outlined in Hydrocarbon Processing, February 1982, page 75 et seq.,
and in U.S. Pat. Nos. 3,763,244; 3,780,128; 4,172,855; 4,218,330;
and 4,950,822. The usual process essentially comprises catalytic
oligomerization of short chain linear alpha olefins (suitably
obtained by catalytic treatment of ethylene). The poly-a-olefins
used as carriers will usually have a viscosity (measured at
100.degree. C.) in the range of 2 to 20 centistokes (cSt).
Preferably, the poly-.alpha.-olefin has a viscosity of at least 8
cSt, and most preferably about 10 cSt at 100.degree. C.
[0053] Suitable poly (oxyalkylene) compounds for the carrier fluids
may be fuel-soluble compounds which can be represented by the
following formula
R.sub.A-(R.sub.B--O).sub.w--R.sub.C
wherein R.sub.A is typically a hydrogen, alkoxy, cycloalkoxy,
hydroxy, amino, hydrocarbyl (e.g., alkyl, cycloalkyl, aryl,
alkylaryl, aralkyl, etc.), amino-substituted hydrocarbyl, or
hydroxy-substituted hydrocarbyl group, R.sub.B is an alkylene group
having 2 to 10 carbon atoms (preferably 2-4 carbon atoms), Rc is
typically a hydrogen, alkoxy, cycloalkoxy, hydroxy, amino,
hydrocarbyl (e.g., alkyl, cycloalkyl, aryl, alkylaryl, aralkyl,
etc.), amino-substituted hydrocarbyl, or hydroxy-substituted
hydrocarbyl group, and w is an integer from 1 to 500 and preferably
in the range of from 3 to 120 representing the number (usually an
average number) of repeating alkyleneoxy groups. In compounds
having multiple --R.sub.B--O-- groups, R.sub.B can be the same or
different alkylene group and where different, can be arranged
randomly or in blocks. Preferred poly (oxyalkylene) compounds are
monools comprised of repeating units formed by reacting an alcohol
with one or more alkylene oxides, preferably one alkylene oxide,
more preferably propylene oxide or butylene oxide.
[0054] The average molecular weight of the poly (oxyalkylene)
compounds used as carrier fluids is preferably in the range of from
about 500 to about 3000, more preferably from about 750 to about
2500, and most preferably from above about 1000 to about 2000.
[0055] One useful sub-group of poly (oxyalkylene) compounds is
comprised of the hydrocarbyl-terminated poly(oxyalkylene) monools
such as are referred to in the passage at column 6, line 20 to
column 7 line 14 of U.S. Pat. No. 4,877,416 and references cited in
that passage, said passage and said references being fully
incorporated herein by reference.
[0056] Another sub-group of poly (oxyalkylene) compounds includes
one or a mixture of alkylpoly (oxyalkylene)monools which in its
undiluted state is a gasoline-soluble liquid having a viscosity of
at least about 70 centistokes (cSt) at 40.degree. C. and at least
about 13 cSt at 100.degree. C. Of these compounds, monools formed
by propoxylation of one or a mixture of alkanols having at least
about 8 carbon atoms, and more preferably in the range of about 10
to about 18 carbon atoms, are particularly preferred.
[0057] The poly (oxyalkylene) carriers may have viscosities in
their undiluted state of at least about 60 cSt at 40.degree. C. (in
other approaches, at least about 70 cSt at 40.degree. C.) and at
least about 11 cSt at 100.degree. C. (more preferably at least
about 13 cSt at 100.degree. C.). In addition, the poly
(oxyalkylene) compounds used in the practice of this invention
preferably have viscosities in their undiluted state of no more
than about 400 cSt at 40.degree. C. and no more than about 50 cSt
at 100.degree. C. In other approaches, their viscosities typically
do not exceed about 300 cSt at 40.degree. C. and typically do not
exceed about 40 cSt at 100.degree. C.
[0058] Preferred poly (oxyalkylene) compounds also include poly
(oxyalkylene) glycol compounds and monoether derivatives thereof
that satisfy the above viscosity requirements and that are
comprised of repeating units formed by reacting an alcohol or
polyalcohol with an alkylene oxide, such as propylene oxide and/or
butylene oxide with or without use of ethylene oxide, and
especially products in which at least 80 mole % of the oxyalkylene
groups in the molecule are derived from 1,2-propylene oxide.
Details concerning preparation of such poly(oxyalkylene) compounds
are referred to, for example, in Kirk-Othmer, Encyclopedia of
Chemical Technology, Third Edition, Volume 18, pages 633-645
(Copyright 1982 by John Wiley & Sons), and in references cited
therein, the foregoing excerpt of the Kirk-Othmer encyclopedia and
the references cited therein being incorporated herein by
reference. U.S. Pat. Nos. 2,425,755; 2,425,845; 2,448,664; and
2,457,139 also describe such procedures, and are fully incorporated
herein by reference.
[0059] The poly (oxyalkylene) compounds, when used, typically will
contain a sufficient number of branched oxyalkylene units (e.g.,
methyldimethyleneoxy units and/or ethyldimethyleneoxy units) to
render the poly (oxyalkylene) compound gasoline soluble. Suitable
poly (oxyalkylene) compounds include those taught in U.S. Pat. Nos.
5,514,190; 5,634,951; 5,697,988; 5,725,612; 5,814,111 and
5,873,917, the disclosures of which are incorporated herein by
reference.
[0060] The polyalkenes suitable for use as carrier fluids include
polypropene and polybutene. The polyalkenes may have a
polydispersity (Mw/Mn) of less than 4. In one embodiment, the
polyalkenes have a polydispersity of 1.4 or below. In general,
polybutenes have a number average molecular weight (Mn) of about
500 to about 2000, preferably 600 to about 1000, as determined by
gel permeation chromatography (GPC). Suitable polyalkenes for use
in the present invention are taught in U.S. Pat. No. 6,048,373.
[0061] The polyalkyl-substituted hydroxyaromatic compounds suitable
for use as carrier fluid include those compounds known in the art
as taught in U.S. Pat. Nos. 3,849,085; 4,231,759; 4,238,628;
5,300,701; 5,755,835 and 5,873,917, the disclosures of which are
incorporated herein by reference.
[0062] Definitions
[0063] For purposes of this disclosure, the chemical elements are
identified in accordance with the Periodic Table of the Elements,
CAS version, Handbook of Chemistry and Physics, 75th Ed.
Additionally, general principles of organic chemistry are described
in "Organic Chemistry", Thomas Sorrell, University Science Books,
Sausolito: 1999, and "March's Advanced Organic Chemistry", 5th Ed.,
Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York:
2001, the entire contents of which are hereby incorporated by
reference.
[0064] As used herein, the term "major amount" is understood to
mean an amount greater than or equal to 50 wt. %, for example from
about 80 to about 98 wt. % relative to the total weight of the
composition. Moreover, as used herein, the term "minor amount" is
understood to mean an amount less than 50 wt. % relative to the
total weight of the composition.
[0065] As described herein, compounds may optionally be substituted
with one or more substituents, such as are illustrated generally
above, or as exemplified by particular classes, subclasses, and
species of the disclosure.
[0066] As used herein, an "alkyl" group refers to a saturated
aliphatic hydrocarbon group containing (unless otherwise noted in
this disclosure) 1-12 (e.g., 1-8, 1-6, or 1-4) carbon atoms. An
alkyl group can be straight or branched. Examples of alkyl groups
include, but are not limited to, methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or
2-ethylhexyl. An alkyl group can be substituted (i.e., optionally
substituted) with one or more substituents such as halo, phospho,
cycloaliphatic [e.g., cycloalkyl or cycloalkenyl],
heterocycloaliphatic [e.g., heterocycloalkyl or hetero
cycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl
[e.g., (aliphatic)carbonyl, (cycloaliphatic)carbonyl, or
(heterocycloaliphatic)carbonyl], nitro, cyano, amido [e.g.,
(cycloalkylalkyl)carbonylamino, arylcarbonylamino,
aralkylcarbonylamino, (heterocyclo alkyl)carbonylamino,
(heterocycloalkylalkyl) carbonylamino, heteroarylcarbonylamino,
heteroaralkylcarbonylamino alkylaminocarbonyl,
cycloalkylaminocarbonyl, heterocyclo alkylaminocarbonyl,
arylaminocarbonyl, or heteroarylaminocarbonyl], amino [e.g.,
aliphaticamino, cycloaliphaticamino, or heterocycloaliphaticamino],
sulfonyl [e.g., aliphatic-SO.sub.2--], sulfinyl, sulfanyl, sulfoxy,
urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl,
cycloaliphaticoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy,
aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or
hydroxy. Without limitation, some examples of substituted alkyls
include carboxyalkyl (such as HOOC-alkyl, alkoxy carbonylalkyl, and
alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl,
acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (such
as (alkyl-SO.sub.2-amino)alkyl), aminoalkyl, amidoalkyl,
(cycloaliphatic)alkyl, or haloalkyl.
[0067] As used herein, an "alkenyl" group refers to an aliphatic
carbon group that contains (unless otherwise noted in this
disclosure) 2-8 (e.g., 2-12, 2-6, or 2-4) carbon atoms and at least
one double bond. Like an alkyl group, an alkenyl group can be
straight or branched. Examples of an alkenyl group include, but are
not limited to allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An
alkenyl group can be optionally substituted with one or more
substituents such as halo, phospho, cycloaliphatic [e.g.,
cycloalkyl or cycloalkenyl], heterocycloaliphatic [e.g.,
heterocycloalkyl or hetero cycloalkenyl], aryl, heteroaryl, alkoxy,
aroyl, heteroaroyl, acyl [e.g., (aliphatic) carbonyl,
(cycloaliphatic)carbonyl, or (heterocycloaliphatic)carbonyl],
nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino,
arylcarbonylamino, aralkylcarbonylamino, (hetero cycloalkyl)
carbonylamino, (heterocyclo alkylalkyl) carbonylamino,
heteroarylcarbonylamino, heteroaralkylcarbonylamino
alkylaminocarbonyl, cycloalkylaminocarbonyl, hetero cyclo
alkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl],
amino [e.g., aliphaticamino, cycloaliphaticamino, heterocyclo
aliphaticamino, or aliphaticsulfonylamino], sulfonyl [e.g.,
alkyl-SO.sub.2--, cycloaliphatic-SO.sub.2--, or aryl-SO.sub.2--],
sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide,
oxo, carboxy, carbamoyl, cycloaliphaticoxy,
heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy,
heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.
Without limitation, some examples of substituted alkenyls include
cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl,
aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (such as
(alkyl-SO.sub.2-amino)alkenyl), aminoalkenyl, amidoalkenyl,
(cycloaliphatic)alkenyl, or haloalkenyl.
[0068] A hydrocarbyl group refers to a group that has a carbon atom
directly attached to a remainder of the molecule and each
hydrocarbyl group is independently selected from hydrocarbon
substituents, and substituted hydrocarbon substituents may contain
one or more of halo groups, hydroxyl groups, alkoxy groups,
mercapto groups, nitro groups, nitroso groups, amino groups,
sulfoxy groups, pyridyl groups, furyl groups, thienyl groups,
imidazolyl groups, sulfur, oxygen and nitrogen, and wherein no more
than two non-hydrocarbon substituents are present for every ten
carbon atoms in the hydrocarbyl group.
[0069] As used herein, fuel-soluble generally means that the
substance should be sufficiently soluble (or dissolve) at about
20.degree. C. in the base fuel at least at the minimum
concentration required for the substance to serve its intended
function. Preferably, the substance will have a substantially
greater solubility in the base fuel. However, the substance need
not dissolve in the base fuel in all proportions.
[0070] The number average molecular weight (Mn) for any approach,
aspect, embodiment or Example herein may be determined with a gel
permeation chromatography (GPC) instrument obtained from Waters or
the like instrument and data as processed with Waters Empower
Software or the like software. The GPC instrument may be equipped
with a Waters Separations Module and Waters Refractive Index
detector (or the like optional equipment). The GPC operating
conditions may include a guard column, 4 Agilent PLgel columns
(length of 300.times.7.5 mm; particle size of 5.mu., and pore size
ranging from 100-10000 .ANG.) with the column temperature at about
40.degree. C. Unstabilized HPLC grade tetrahydrofuran (THF) may be
used as solvent, at a flow rate of 1.0 mL/min. The GPC instrument
may be calibrated with commercially available polystyrene (PS)
standards having a narrow molecular weight distribution ranging
from 500-380,000 g/mol. The calibration curve can be extrapolated
for samples having a mass less than 500 g/mol. Samples and PS
standards can be in dissolved in THF and prepared at concentration
of 0.1-0.5 wt. % and used without filtration. GPC measurements are
also described in U.S. Pat. No. 5,266,223, which is incorporated
herein by reference. The GPC method additionally provides molecular
weight distribution information; see, for example, W. W. Yau, J. J.
Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography", John Wiley and Sons, New York, 1979, also
incorporated herein by reference.
[0071] A better understanding of the present disclosure and its
many advantages may be clarified with the following examples. The
following examples are illustrative and not limiting thereof in
either scope or spirit. Those skilled in the art will readily
understand that variations of the components, methods, steps, and
devices described in these examples can be used. Unless noted
otherwise or apparent from the context of discussion, all
percentages, ratios, and parts noted in this disclosure are by
weight.
EXAMPLES
Example 1
[0072] Experiments were performed to evaluate the clean-up
performance of various fuel additives of the present disclosure
when combusted in gasoline engines configured to operate at high
fuel pressure. FIG. 1 illustrates the percent clean-up of a
gasoline engine injecting a fuel between about 580 to about 1,960
psi with three different fuel injector cleaning additives: about
3.8 ppmw of oleyl dimethyl amino propyl amine betaine, about 7.6
ppmw of a PIBSA-TEPA additive, and an inventive synergistic
combination of 3.8 ppmw of the betaine combined with about 7.6 ppmw
of the PIBSA-TEPA cleaning additives together (1:2 ratio).
[0073] As shown in FIG. 1, while the betaine cleaning additive
alone provided a modest level of fuel injector clean-up when
combusted in a gasoline engine operated at about 580 to about 1,960
psi fuel injection, the PIBSA-TEPA additive provided no clean-up
performance in the high pressure fuel at 7.6 ppmw. However, adding
the PIBSA-TEPA in combination with the betaine (2:1 ratio)
demonstrated a profound increase in the fuel injector clean-up
performance when operating at the high gasoline fuel injection
pressures. Given that the PIBSA-TEPA additive had no clean-up
performance in the high pressure gasoline engine at 7.6 ppmw, it
was not expected that a combination of the PIBSA-TEPA and the
betaine would result in an increased clean-up rate relative to the
betaine alone. This synergistic combination of the two additives
delivered about double the clean-up rate of the betaine alone by
2000 miles of operating the engine at high fuel pressures.
[0074] The high pressure gasoline engine testing was evaluated for
the additives ability to clean-up fouled injectors in a high
pressure fuel injection engine using the procedure set forth in
Shanahan, C., Smith, S., and Sears, B., "A General Method for
Fouling Injectors in Gasoline Direct Injection Vehicles and the
Effects of Deposits on Vehicle Performance," SAE Int. J. Fuels
Lubr. 10(3):2017, doi:10.4271/2017-01-2298, which is incorporated
herein by reference in its entirety and discussed further below.
While the tests herein utilized a Kia Optima engine, the
observations and results are applicable to other vehicle makes,
models and other high pressure engines.
[0075] The testing involved the use of a fuel blend to accelerate
the dirty-up phase or injector fouling of the engine. The
accelerated EO gasoline blend included 409 ppmw of di-tert-butyl
disulfide (DTBDS, contributing about 147 ppmw active sulfur to the
fuel) and 286 ppmw of tert-butyl hydrogen peroxide (TBHP). The test
involved running a 2013 Kia Optima having a 2.4L, 16 valve, inline
4 gasoline high pressure direct injection engine on a mileage
accumulation dynamometer. The engine was run using the "Quad 4"
drive cycle as set forth in the above noted SAE paper (SAE
2017-01-2298) and as set forth in Table 1 below. Injector
cleanliness was measured using Long Term Fuel Trim (LTFT) as
reported by the vehicle engine control unit (ECU) and was measured
relative to the accumulated mileage. Results of the testing are
shown in FIG. 1. Clean-up percentage is the change of LTFT from the
start of test relative to the LTFT at the predetermined mile test
points.
TABLE-US-00001 TABLE 1 Quad 4 Drive Cycle Time (min) 0 0.5 11.75
11.95 28.35 28.55 39.5 40 64.5 64.75 82.75 83 99.4 100 105 Speed
(mph) 0 40 40 55 55 40 40 55 55 25 25 55 55 0 0 Acceleration 1.3
1.3 -1.3 0.5 -2 2 -1.5 (mph/sec) Steady State 11.25 16.4 10.95 24.5
18 16.4 5 Duration (min)
[0076] It is to be understood that while the fuel additives,
compositions, and methods of this disclosure have been described in
conjunction with the detailed description thereof and summary
herein, the foregoing description is intended to illustrate and not
limit the scope of the disclosure, which is defined by the scope of
the appended claims. Other aspects, advantages, and modifications
are within the scope of the claims. It is intended that the
specification and examples be considered as exemplary only, with a
true scope of the disclosure being indicated by the following
claims.
[0077] Other embodiments of the present disclosure will be apparent
to those skilled in the art from consideration of the specification
and practice of the embodiments disclosed herein. As used
throughout the specification and claims, "a" and/or "an" may refer
to one or more than one. Unless otherwise indicated, all numbers
expressing quantities of ingredients, properties such as molecular
weight, percent, ratio, reaction conditions, and so forth used in
the specification are to be understood as being modified in all
instances by the term "about," whether or not the term "about" is
present. Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the specification are
approximations that may vary depending upon the desired properties
sought to be obtained by the present disclosure. At the very least,
and not as an attempt to limit the application of the doctrine of
equivalents to the scope of the claims, each numerical parameter
should at least be construed in light of the number of reported
significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting
forth the broad scope of the disclosure are approximations, the
numerical values set forth in the specific examples are reported as
precisely as possible. Any numerical value, however, inherently
contains certain errors necessarily resulting from the standard
deviation found in their respective testing measurements.
[0078] It is to be understood that each component, compound,
substituent or parameter disclosed herein is to be interpreted as
being disclosed for use alone or in combination with one or more of
each and every other component, compound, substituent or parameter
disclosed herein.
[0079] It is further understood that each range disclosed herein is
to be interpreted as a disclosure of each specific value within the
disclosed range that has the same number of significant digits.
Thus, for example, a range from 1 to 4 is to be interpreted as an
express disclosure of the values 1, 2, 3 and 4 as well as any range
of such values. It is also further understood that any range
between the endpoint values within a described range is also
discussed herein. Thus, a range from 1 to 4 also means a range from
1 to 3, 1 to 2, 2 to 4, 2 to 3, and so forth.
[0080] It is further understood that each lower limit of each range
disclosed herein is to be interpreted as disclosed in combination
with each upper limit of each range and each specific value within
each range disclosed herein for the same component, compounds,
substituent or parameter. Thus, this disclosure to be interpreted
as a disclosure of all ranges derived by combining each lower limit
of each range with each upper limit of each range or with each
specific value within each range, or by combining each upper limit
of each range with each specific value within each range.
[0081] Furthermore, specific amounts/values of a component,
compound, substituent or parameter disclosed in the description or
an example is to be interpreted as a disclosure of either a lower
or an upper limit of a range and thus can be combined with any
other lower or upper limit of a range or specific amount/value for
the same component, compound, substituent or parameter disclosed
elsewhere in the application to form a range for that component,
compound, substituent or parameter.
* * * * *