TECHNICAL FIELD
[0001] This disclosure is directed to fuel additives for spark-ignition engines providing
enhanced engine and/or injector performance, to fuel compositions including such additives,
and to methods for using such fuel additives in a fuel composition.
BACKGROUND
[0002] Fuel compositions for vehicles are continually being improved to enhance various
properties of the fuels in order to accommodate their use in newer, more advanced
engines including both gasoline port fuel injected engines as well as gasoline direct
injected engines. Often, improvements in fuel compositions center around improved
fuel additives and other components used in the fuel. For example, friction modifiers
may be added to fuel to reduce friction and wear in the fuel delivery systems of an
engine. Other additives may be included to reduce the corrosion potential of the fuel
or to improve the conductivity properties. Still other additives may be blended with
the fuel to improve fuel economy. Engine and fuel delivery system deposits represent
another concern with modern combustion engines, and therefore other fuel additives
often include various deposit control additives to control and/or mitigate engine
deposit problems. Thus, fuel compositions typically include a complex mixture of additives.
[0003] However, there remain challenges when attempting to balance such a complex assortment
of additives. For example, some of the conventional fuel additives may be beneficial
for one characteristic or one type of engine, but at the same time be detrimental
to another characteristic of the fuel. In some instances, fuel additives effective
in gasoline port fuel injection engines do not necessarily provide comparable performance
in gasoline direct injection engines and vice versa. In yet other circumstances, fuel
additives often require an unreasonably high treat rate to achieve desired effects,
which tends to place undesirable limits on the available amounts of other additives
in the fuel composition. Yet other fuel additives tend to be expensive and/or difficult
to manufacture or incorporate in fuels. Such shortcomings are particularly true in
the context of quaternary ammonium salt fuel additives that are often difficult or
costly to manufacture and/or require relatively high treat rates for performance.
SUMMARY
[0004] In one aspect, a method of providing improved engine performance is provided herein.
In one embodiment or approach, a fuel additive package for a spark-ignition engine
is described herein to provide the improved engine performance and includes (i) a
Mannich detergent including the reaction product of a hydrocarbyl-substituted phenol,
one or more aldehydes, and one or more amines and (ii) a quaternary ammonium internal
salt obtained from amines or polyamines that is substantially devoid of any free anion
species.
[0005] In other approaches or embodiments, the fuel additive package described above may
include one or more optional features or embodiments in any combination. These optional
features or embodiments may include one or more of the following: wherein the fuel
additive package further includes an alkoxylated alcohol; and/or wherein a weight
ratio of the alkoxylated alcohol to the Mannich detergent is about 0.8 or less; and/or
wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol
or an alkylphenol with an alkylene oxide selected from ethylene oxide, propylene oxide,
butylene oxide, copolymers thereof, or combinations thereof; and/or wherein a weight
ratio of the Mannich detergent to the quaternary ammonium internal salt is about 5:1
to about 100:1; and/or wherein the Mannich detergent has the structure of Formula
I:
wherein R
1 is hydrogen or a C1 to C4 alkyl group, R
2 is a hydrocarbyl group having a number average molecular weight of about 500 to about
3000, R
3 is a C1 to C4 alkylene or alkenyl group, and R
4 and R
5 are, independently, hydrogen, a C1 to C12 alkyl group, or a C1 to C4 alkyl amino
C1-C12 alkyl group; and/or wherein the quaternary ammonium internal salt has the structure
of Formula II
wherein Rand R' are, independently, alkylene linkers having 1 to 10 carbon atoms;
R
8 is a C12 to C100 alkylene, alkene, or hydrocarbyl group or an aryl group or optionally
substituted aryl group; each R
9 is, independently, a linear or branched C1 to C4 alkyl group; and R
10 is a hydrogen atom or a C1 to C4 alkyl group; and/or wherein the alkoxylated alcohol
is a polyether having the structure of Formula III:
wherein R
6 is an aryl group or a linear, branched, or cyclic aliphatic group having 5 to 50
carbons, R
7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and/or wherein the
fuel additive package includes about 20 to about 60 weight percent of the Mannich
detergent, about 1 to about 15 weight percent of the quaternary ammonium internal
salt, and about 5 to about 30 weight percent of the alkoxylated alcohol; and/or further
comprising a succinimide detergent 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; and/or wherein the fuel additive package
includes about 0.1 to about 10 weight percent of the succinimide detergent; and/or
wherein the succinimide detergent is a hydrocarbyl substituted mono-succinimide detergent,
a hydrocarbyl substituted bis-succinimide detergent, or a combination thereof; and/or
further comprising one or more of a demulsifier, a corrosion inhibitor, an antiwear
additive, an antioxidant, a metal deactivator, an antistatic additive, a dehazer,
an antiknock additive, a lubricity additive, and/or a combustion improver.
[0006] In other approaches or embodiments, the disclosure herein also describes a gasoline
fuel composition comprising about 40 to about 750 ppmw of a fuel additive package
as described in any of the embodiments from the previous two paragraphs and including
about 15 to about 300 ppmw of the Mannich detergent, about 0.1 to about 10 ppmw of
the quaternary ammonium internal salt, and about 2 to about 90 ppmw of the alkoxylated
alcohol.
[0007] The gasoline fuel composition of the previous paragraph may also include other optional
features or embodiments in any combination. These optional feature or embodiments
of the gasoline fuel composition may include one or more of the following: wherein
intake valve deposits, as measured pursuant to one of ASTM D6201, or ASTM D5500 are
reduced when the gasoline fuel composition is combusted in a spark-ignition engine
as compared to combusting a gasoline fuel composition including the aminophenol detergent
and/or the alkoxylated alcohol and being devoid of the quaternary ammonium internal
salt; and/or wherein the spark-ignition engine is a gasoline direct or port fuel injection
engine.
[0008] In yet other approaches or embodiments, a method of improving the injector performance
of a gasoline direct injection (GDI) engine is described herein. The method includes
operating the gasoline direct injection engine on a fuel composition containing a
major amount of a gasoline fuel and a minor amount of the fuel additive package as
described by any embodiment set forth in this Summary, and wherein the fuel additive
package in the gasoline fuel improves the injector performance of the gasoline direct
injection engine. Also provided herein is the use of a fuel additive package as described
by any embodiment herein or any embodiment of a fuel composition herein for improving
the injector performance of a gasoline direct injection engine.
[0009] The method or the use of the previous paragraph may include optional steps, features,
or limitations in any combination thereof. Approaches or embodiments of the method
or use may include one or more of the following: wherein the improved injector performance
is one of improved fuel flow, improved fuel economy, improved engine efficiency, or
combinations thereof; and/or wherein the improved injector performance is measured
by one of injector pulse width, injection duration, injector flow, or combinations
thereof.
BRIEF DESCRIPTION OF DRAWING FIGURES
[0010]
FIG. 1 is a graph showing percent of injector fouling in a base fuel and an additized
fuel;
FIG. 2 is a graph showing Long Term Fuel Trim (LTFT) of a base fuel and an additized
fuel; and
FIG. 3 is a graph showing Long Term Fuel Trim (LTFT) of Inventive 5 and Comparatives
3 and 4.
DETAILED DESCRIPTION
[0011] The present disclosure provides fuel additives including combinations of Mannich
detergents and quaternary ammonium salts and, in particular, Mannich detergents and
hydrocarbyl-substituted quaternary ammonium internal salts discovered effective to
provide improved engine and/or injector performance in both port fuel injection (PFI)
engines as well as gasoline direct injection (GDI) engines. The fuel additives, in
some approaches, may also include alkoxylated alcohols and, when included, certain
ratios of the alkoxylated alcohol to the Mannich detergent. Also provided herein are
fuel compositions including the novel fuel additive combinations and methods of using
or combusting a fuel including the fuel additive combinations herein to achieve the
improved engine and/or injector performance.
[0012] In aspects or embodiments of this disclosure, improved engine and/or injector performance
of the fuel additive combinations herein may include one or more of controlling or
reducing fuel injector deposits, controlling or reducing intake valve deposits, controlling
or reducing combustion chamber deposits and/or controlling or reducing intake valve
sticking. Improved injector performance may also be one or more of improved fuel flow,
improved fuel economy, and/or improved engine efficiency as determined via one or
more of injector pulse width, injection duration, and/or injector flow.
Mannich Detergent
[0013] In one aspect, the fuel additives and fuels herein include a Mannich detergent. Suitable
Mannich detergents include the reaction product(s) of an alkyl-substituted hydroxyaromatic
or phenol compound, aldehyde, and amine as discussed more below.
[0014] In one approach, the alkyl substituents of the hydroxyaromatic compound may include
long chain hydrocarbyl groups on a benzene ring of the hydroxyaromatic compound and
may be derived from an olefin or 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,
in some approaches, may also have a polydispersity (weight average molecular weight/number
average molecular weight) of about 1 to about 10 (in other instances, about 1 to 4
or about 1 to about 2) as determined by GPC using polystyrene as reference.
[0015] The alkylation of the hydroxyaromatic or phenol compound is typically performed in
the presence of an alkylating catalyst at a temperature in the range of about 0 to
about 200°C, preferably 0 to 100°C. Acidic catalysts are generally used to promote
Friedel-Crafts alkylation. Typical catalysts used in commercial production include
sulphuric acid, BF
3, aluminum phenoxide, methanesulphonic acid, cationic exchange resin, acidic clays
and modified zeolites.
[0016] Polyolefins suitable for forming the alkyl-substituted hydroxyaromatic compounds
of the Mannich detergents 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 a copolymer
molecule contains at least 50% by weight, of butylene and/or isobutylene and/or propylene
units. Any comonomers polymerized with propylene or butenes may be aliphatic and can
also contain non-aliphatic groups, e.g., styrene, o-methylstyrene, p-methylstyrene,
divinyl benzene and the like if needed. Thus, the resulting polymers and copolymers
used in forming the alkyl-substituted hydroxyaromatic compounds are substantially
aliphatic hydrocarbon polymers.
[0017] Polybutylene is preferred for forming the hydrocarbyl-substituted hydroxyaromatic
or phenol compounds herein. 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
3 catalysts. The preparation of such polyisobutenes in which the methylvinylidene isomer
comprises a high percentage of the total composition is described in
US 4,152,499 and
US 4,605,808, which are both incorporated herein by reference.
[0018] The Mannich detergent, in some approaches or embodiments, may be made from an alkylphenol
or alkylcresol. However, other phenolic compounds may be used including 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.,
polypropyl phenol, polybutylphenol, polypropylcresol and polybutylcresol, wherein
the alkyl group has a number average molecular weight of about 500 to about 3000 or
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.
[0019] The preferred configuration of the 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 forming this detergent additive. The alkyl substituents may contain some
residual unsaturation, but in general, are substantially saturated alkyl groups.
[0020] In approaches or embodiments, representative amine reactants suitable to form the
Mannich detergent herein 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 one embodiment, the alkylene polyamine is a polyethylene polyamine. Suitable
alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylene pentamine and mixtures of such amines having nitrogen contents corresponding
to alkylene polyamines of the formula H
2N--(A-NH--)
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.
[0021] 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"-tetraalkyltrialkylene
tetramines (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'-dialkylamine, 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-alkylene diamine, 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.
Exemplary amines may include N,N-dimethyl-1,3-propanediamine and/or N-methyl piperazine.
[0022] 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-propane
diamine-, N-(
tert-butyl)-1-methyl-1,2-ethanediamine, N-(tert-butyl)-1-methyl-1,3-propane diamine, and
3,5-di(tert-butyl)aminoethylpiperazine.
[0023] In approaches or embodiments, representative aldehydes for use in the preparation
of the Mannich detergents herein 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.
[0024] 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°C to about 200°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. Suitable Mannich base detergents include those
detergents taught in
US 4,231,759;
US 5,514,190;
US 5,634,951;
US 5,697,988;
US 5,725,612; and
5,876,468, the disclosures of which are incorporated herein by reference.
[0025] In other approaches or embodiments, suitable Mannich detergents for the fuel additives
herein may have a structure of Formula I below:
wherein R
1 is hydrogen or a C1 to C4 alkyl group, R
2 is a hydrocarbyl group having a number average molecular weight of about 500 to about
3000 (or about 500 to about 2100 or about 500 to about 1800), R
3 is a C1 to C4 alkylene or alkenyl linking group, and R
4 and R
5 are, independently, hydrogen, a C1 to C12 alkyl group, or a C1 to C4 alkyl amino
C1-C12 alkyl group.
[0026] A fuel additive or additive package may include about 10 to about 70 weight percent
of the above-described Mannich detergent, about 20 to about 60 weight percent of the
Mannich detergent, or about 30 to about 50 weight percent of the Mannich detergent
(based on the total weight of the active Mannich detergent in the fuel additive).
When blended into a gasoline fuel, the fuel composition may include about 15 ppmw
to about 300 ppmw of the above-described Mannich detergent, about 25 ppmw to about
155 ppmw, or about 55 ppmw to about 125 ppmw of the Mannich detergent in the fuel
composition (active Mannich detergent treat rates).
Quaternary Ammonium Internal Salt:
[0027] In another aspect, the fuel additives or fuels herein include a quaternary ammonium
salt and, preferably, a quaternary ammonium internal salt or betaine compound. In
approaches or embodiments, the quaternary ammonium salt additive may be any hydrocarbyl
substituted quaternary ammonium internal salt (or betaine) obtained from amines or
polyamines that are substantially devoid of any free anion species. For example, such
additive may be made by reacting a tertiary amine of the structure below
wherein each R group of the above structure is independently selected from hydrocarbyl
groups containing from 1 to 200 carbon atoms with a halogen substituted C2-C8 carboxylic
acid, ester, amide, or salt thereof. In approaches, what is generally to be avoided
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.
[0028] 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 substantial amounts of free anions or anions that
are ionically bound to the product. In one embodiment, "substantially devoid" means
a range from 0 to less than about 2 weight percent of free anion species, less than
about 1.5 weight percent, less than about 1 weight percent, less than about 0.5 weight
percent, or none.
[0029] In another approach or embodiment, a tertiary amine including monoamines and polyamines
may be reacted with the halogen substituted acetic acid, ester, or other derivative
thereof to provide the quaternary ammonium internal salt additive herein. Suitable
tertiary amine compounds are those of structure above wherein each of R group is independently
selected, as noted above, from hydrocarbyl groups containing from 1 to 200 carbon
atoms. Each hydrocarbyl group R 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. In some approaches, the tertiary amine may
be the reaction product of a diamine or triamine with one tertiary amine and a hydrocarbyl
substituted carboxylic acid. In other approaches, 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,N-dimethylpropane diamine, 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.
In one approach or embodiment, a suitable quaternary ammonium internal salt additive
may be the internal salts of oleyl amidopropyl dimethylamino or oleyl dimethyl amine.
[0030] 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.
[0031] The halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof for
use in making the quaternary internal salt 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, ester,
or salt thereof may be selected from chloroacetic acid or esters thereof 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.
[0032] In yet other approaches, internal salts of the mixtures herein may be made according
to the foregoing procedures and may include, but are not limited to (1) hydrocarbyl
substituted compounds of the formula R"-NMe
2CH
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.
[0033] In yet another approach, the quaternary ammonium internal salt of the fuel additives
and fuels herein is an internal salt or betaine compound having the structure of Formula
II below:
wherein Rand R' of the structure above are independently alkylene linkers having 1
to 10 carbon atoms (in other approaches 1 to 3 carbon atoms); R
8 is a saturated alkylene, unsaturated alkene, or a linear, branched, or cyclic hydrocarbyl
group or optionally a substituted or unsubstituted C12 to C100 hydrocarbyl group,
or an aryl group or optionally substituted aryl group (in one approach, R
8 is a C8 to C20 hydrocarbyl group); each R
9 is independently a linear or branched C1 to C4 alkyl group; and R
10 is a hydrogen atom or a C1 to C4 alkyl group. The internal salts of Formula II may
also be substantially devoid of free anion species as discussed above.
[0034] In another approach, the quaternary ammonium salt additive includes the compound
of Formula II above wherein R is a propylene linker, R' is a methylene linker, R
8 is a C8 to C20 hydrocarbyl group, each R
9 is a methyl group, and R
10 is hydrogen. In yet other approaches, the quaternary ammonium salt internal salt
is selected from oleyl amidopropyl dimethylamine internal salts or oleyl dimethylamino
internal salts. In some approaches, such additive may be substantially devoid of free
anion species as noted above.
[0035] An exemplary reaction scheme of preparing the quaternary ammonium internal salt is
shown below in the exemplary process of Reaction Scheme I; of course, other methods
of preparing the first quaternary ammonium salt additives described herein may also
be utilized:
In the reaction scheme above, R
8 may be as described above or, in one approach, an alkyl group such as a C12 to C100
hydrocarbyl group; R and R' are independently alkylene linkers having 1 to 10 carbon
atoms; each R
9 is independently a alkyl group or a linear or branched C
1 to C
4 group; and R‴ is an alkyl group or hydrogen.
[0036] A fuel additive herein may include about 1 to about 15 weight percent of the quaternary
ammonium internal salt, about 1 to about 10 weight percent of the quaternary ammonium
internal salt, or about 1.5 to about 5 weight percent of the quaternary ammonium internal
salt (based on the total active weight of the quaternary ammonium salt in the fuel
additive). When blended into a gasoline fuel, the fuel may include about about 0.1
to about 20 ppmw of the active quaternary ammonium internal salt, about 0.1 to about
10 ppmw, about 0.3 ppmw to about 5 ppmw, or about 1 ppmw to about 3 ppmw of the active
quaternary ammonium internal salt in the fuel.
Alkoxylated Alcohol
[0037] The fuel additives or fuels of the present disclosure may also include one or more
optional alkoxylated alcohols. The alkoxylated alcohol is preferably a polyether prepared
by reacting an long chain alkyl alcohol or alkylphenol with an alkylene oxide. By
one approach, the alkoxylated alcohol may be one or more hydrocarbyl-terminated or
hydrocarbyl-capped poly(oxyalkylene) polymers. The hydrocarbyl moieties thereof may
be aryl or aliphatic groups, and preferably, aliphatic chains that are linear, branched
or cyclic, and most preferably are linear aliphatic chains. In one approach, the alkoxylated
alcohols may have the structure of Formula IIIa, IIIb, and/or IIIc below:
wherein R
6 is an aryl group or a linear, branched, or cyclic aliphatic group and preferably
having 5 to 50 carbons (or 5 to 30 carbons) or may be a -C
mH
2m+1 group where m is an integer of 12 or more, R
7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100 (or as further discussed
below).
[0038] In some approaches, suitable alkoxylated alcohols are derived from lower alkylene
oxides selected from the group consisting of ethylene oxide, propylene oxide, butylene
oxide, copolymers thereof, and combinations thereof. Preferably, the lower alkylene
oxides are propylene oxide or butylene oxide or copolymers of ethylene oxide, propylene
oxide, and butylene oxide (as well as any combinations thereof). In another approach,
the alkylene oxides are propylene oxide. Any copolymers of such alkylene oxides may
be random or block copolymers. In one approach, the alkoxylated alcohols may be terminated
or capped with an aryl, alkyl, or hydrocarbyl group and may include one or more aryl
or linear, branched, or cyclic aliphatic C5 to C30 terminated alkoxylated alcohols,
and in other approaches, a C16 to C18 (or blend thereof) terminated alkoxylated alcohol
having 5 to 100, 10 to 80, 20 to 50, or 22 to 32 repeating units of the alkylene oxide
therein (that is, n integer of the formula above). In some approaches, the alkoxylated
alcohols may have a weight average molecular weight of about 1300 to about 2600 and,
in other approaches, about 1600 to about 2200.
[0039] In some approaches, the aliphatic hydrocarbyl terminated alkoxylated alcohols may
include about 20 to about 70 weight percent (in another approach, about 30 to about
50 weight percent) of an aliphatic C16 alkoxylated alcohol having 24 to 32 repeating
units of alkoxylene oxide and/or may include about 80 to about 30 weight percent (in
another approach, about 50 to about 70 weight percent) of an aliphatic C18 alkoxylated
alcohol having 24 to 32 repeating units of alkoxylene oxide. In other approaches,
the fuel additives herein, if including an alkoxylated alcohol, may also have about
8 percent or less (in other approaches, about 6 percent or less, and in yet other
approaches, about 4 percent or less) of C20 or greater alkoxylated alcohols and/or
about 4 weight percent or less (in or other approaches about 2 weight percent or less,
and in yet other approaches, about 1 percent or less) of C14 or lower alkoxylated
alcohols.
[0040] The aryl or hydrocarbyl-capped poly(oxyalkylene) alcohols may be produced by the
addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, or the
butylene oxides, to a desired hydroxy compound R-OH (that is, a starter alcohol) under
polymerization conditions, wherein R is the aryl or hydrocarbyl group having either
5 to 30 carbons or other chain length as noted above and which caps the poly(oxyalkylene)
chain. The alkoxylated alcohols can be prepared by any starter alcohol that provides
the desired polyol distribution. By one approach, the alkoxylated alcohol can be prepared
by reacting a saturated linear or branched alcohol of the desired hydrocarbon size
with the selected alkylene oxide and a double metal or basic catalyst. In one approach,
the alkoxylated alcohol may be nonylphenol alkyxylated alcohol such as nonylphenol
propoxylated alcohol.
[0041] In other approaches, in the polymerization reaction a single type of alkylene oxide
may be employed, e.g., propylene oxide, in which case the product is a homopolymer,
e.g., a poly(oxyalkylene) propanol. However, copolymers are equally satisfactory and
random or block copolymers are readily prepared by contacting the hydroxyl-containing
compound with a mixture of alkylene oxides, such as a mixture of ethylene, propylene,
and/or butylene oxides. Random polymers are more easily prepared when the reactivities
of the oxides are relatively equal. In certain cases, when ethylene oxides is copolymerized
with other oxides, the higher reaction rate of ethylene oxide makes the preparation
of random copolymers difficult. In either case, block copolymers can be prepared.
Block copolymers are prepared by contacting the hydroxyl-containing compound with
first one alkylene oxide, then the others in any order, or repetitively, under polymerization
conditions. In one example, a particular block copolymer may be represented by a polymer
prepared by polymerizing propylene oxide on a suitable monohydroxy compound to form
a poly(oxypropylene) alcohol and then polymerizing butylene oxide on the poly(oxyalkylene)
alcohol.
[0042] A fuel additive or fuel herein, when included, may include about 5 to about 30 weight
percent of the alkoxylated alcohol, about 8 to about 20 weight percent of the alkoxylated
alcohol, or about 10 to about 15 weight percent of the alkoxylated alcohol (based
on the active alkoxylated alcohol in the fuel additive). When blended into a gasoline
fuel, the fuel may include about 2 ppmw to about 150 ppmw of the active alkoxylated
alcohol, 5 to about 150 ppmw, about 8 ppmw to about 50 ppmw, or about 15 ppmw to about
40 ppmw of the alkoxylated alcohol in the fuel.
Succinimide Detergents
[0043] The fuel additives or fuels herein may also include one or more optional hydrocarbyl
substituted dicarboxylic anhydride derivatives, and preferably one or more succinimide
detergents. In one approach, this additive 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. In some embodiments, the hydrocarbyl
substituted dicarboxylic anhydride derivative 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. The detergents may be mono-succinimides,
bis-succinimides, or combinations thereof.
[0044] In some approaches or embodiments, 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
2N-((CHR
1-(CH
2)
q-NH)
r-H, wherein R
1 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.
[0045] In other approaches, the hydrocarbyl substituted dicarboxylic anhydride may be a
hydrocarbyl carbonyl compound of the Formula IV:
where R
10 is a hydrocarbyl group derived from a polyolefin. In some aspects, the hydrocarbyl
carbonyl compound may be a polyalkylene succinic anhydride reactant wherein R
10 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
10 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
10 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.
[0046] The R
10 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
10 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
10 polyalkenyl radicals may be formed by any suitable methods, such as by conventional
catalytic oligomerization of alkenes.
[0047] 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
10 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
US 4,152,499, the disclosure of which is herein incorporated by reference in its entirety.
[0048] 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.
[0049] 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°C to about 250°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
US 4,234,435, which is incorporated herein by reference in its entirety.
[0050] 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
2N-((CHR
1-(CH
2)
q-NH)
r-H, wherein R
1 is hydrogen, q is 1 and r is 4.
[0051] In yet further approaches, the hydrocarbyl substituted dicarboxylic anhydride derivative
is a compound of Formula V
wherein R
10 is a hydrocarbyl group (such as polyisobutylene and/or the other above described
R
10 moieties) and R
11 is a hydrogen, an alkyl group, an aryl group, -OH, -NHR
12, or a polyamine, or an alkyl group containing one or more primary, secondary, or
tertiary amino groups. In some approaches, R
11 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 some embodiments, R
10 is a hydrocarbyl group and R
11 is hydrogen, an alkyl group, an aryl group, -OH, -NHR
12, or a polyamine and wherein R12 is a hydrogen or an alkyl group. In other embodiments,
the additive of Formula V includes a hydrocarbyl substituted succinimide derived from
ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine,
pentaethylene hexamine, N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine and combinations
thereof. In still other embodiments, R
4 in the compound of Formula I is a hydrocarbyl group having a number average molecular
weight from about 450 to about 3,000 and R
11 is derived from tetraethylene pentamine and derivatives thereof.
[0052] In yet other approaches R
11 is a compound of Formula VI
wherein A is NR
12 or an oxygen atom, R
12, R
13, and R
14 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
13 and R
14 of Formula VI, together with the nitrogen atom to which they are attached, form a
5 membered ring. In approaches, the succinimide detergent is a hydrocarbyl substituted
mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or
a combination thereof.
[0053] A fuel additive or fuel herein, when included, may include about 0.1 to about 10
weight percent of the active succinimide detergent, about 0.5 to about 8 weight percent
of the succinimide detergent, or about 1 to about 5 weight percent of the succinimide
detergent (based on the total weight of the active succinimide within the fuel additive).
When blended into a gasoline fuel, the fuel may include about 0.5 ppmw to about 20
ppmw of the active succinimide detergent, about 1 ppmw to about 10 ppmw, or about
2 ppmw to about 5 ppmw of the succinimide detergent in the fuel.
Fuel Additive:
[0054] When formulating the fuel compositions of this application, the above described additives
(including at least the Mannich detergent and quaternary ammonium internal salt) may
be employed in amounts sufficient to reduce or inhibit deposit formation in a fuel
system, a combustion chamber of an engine and/or crankcase, and/or within fuel injectors
and within a gasoline direction injection engine and/or a port fuel injection engine.
Such additives may also be provided in amounts to improve injector performance as
described herein. In some aspects, the fuel additive or fuel additive package herein
may include at least the above described Mannich detergent, the quaternary ammonium
internal salt, an optional alkoxylated alcohol, and an optional succinimide detergent.
The fuel additives herein may also include other optional additives as needed for
a particular application and may include as needed one or more of a demulsifier, a
corrosion inhibitor, an antiwear additive, an antioxidant, a metal deactivator, an
antistatic additive, a dehazer, an antiknock additive, a lubricity additive, and/or
a combustion improver.
[0055] In some approaches or embodiments, the fuel additive or additive package herein may
include about 30 to about 60 weight percent of the Mannich detergent and about 1 to
about 15 weight percent of the quaternary ammonium internal salt. In other approaches,
the fuel additive or additive package may also include about 5 to about 20 weight
percent of the alkoxylated alcohol and/or about 0.1 to about 10 weight percent of
the Succinimide detergent.
[0056] In other approaches, a gasoline fuel composition may include about 40 to about 750
ppmw of the fuel additive or additive package herein, in other approaches, about 60
to about 380 ppmw, or about 135 to about 310 ppmw of the above noted fuel additive
package and which provides about 15 to about 300 ppmw of the Mannich detergent and
about 0.1 to about 10 ppmw of the quaternary ammonium internal salt to the fuel. In
other embodiments, the fuel may also include about 2 to about 90 ppmw of the alkoxylated
alcohol and/or about 0.5 to about 20 ppmw of the succinimide detergent. It will also
be appreciated that any endpoint between the above described ranges are also suitable
range amounts as needed for a particular application. The above-described amounts
reflects additives on an active ingredient basis, which means the additives noted
above excludes the weight of (i) unreacted components associated with and remaining
in the product as produced and used, and (ii) solvent(s), if any, used in the manufacture
of the product either during or after its formation.
[0057] In other approaches, the fuel additive package or fuel thereof also has a certain
weight ratio of the alkoxylated alcohol to the Mannich detergent of about 0.8 or less
(i.e., 0.8:1 or less), about 0.6 or less, about 0.5 or less, about 0.4 or less, or
about 0.3 or less, and about 0.1 or more (i.e., 0.1:1), about 0.2 or more, or about
0.3 or more. In yet other approaches, the fuel additive package or fuel thereof may
also have a weight ratio of the Mannich detergent to the quaternary ammonium internal
salt of about 5:1 to about 100:1 or about 20:1 to about 80:1 or about 30:1 to about
75:1 (wherein the weight ratios are active Mannich detergent to the active quaternary
ammonium internal salt).
Other Additives
[0058] One or more optional compounds may be present in the fuel compositions of the disclosed
embodiments. For example, the fuels may contain conventional quantities of cetane
improvers, octane improvers, corrosion inhibitors, cold flow improvers (CFPP additive),
pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers,
amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat
stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate
ignition accelerators, cyclomatic manganese tricarbonyl compounds, carrier fluids,
and the like. In some aspects, the compositions described herein may contain about
10 weight percent or less, or in other aspects, about 5 weight percent or less, based
on the total weight of the additive concentrate, of one or more of the above optional
additives. Similarly, the fuels may contain suitable amounts of conventional fuel
blending components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and
the like.
[0059] In some aspects of the disclosed embodiments, organic nitrate ignition accelerators
that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic
group is saturated, and that contain up to about 12 carbons may be used. Examples
of organic nitrate ignition accelerators that may be used are methyl nitrate, ethyl
nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl
nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl
nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate,
isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate,
dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate,
cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuranyl
nitrate, and the like. Mixtures of such materials may also be used.
[0060] Examples of suitable optional metal deactivators useful in the compositions of the
present application are disclosed in
U.S. Pat. No. 4,482,357, the disclosure of which is herein incorporated by reference in its entirety. Such
metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene
ethylenediamine, disalicylidene propylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.
[0061] Suitable optional cyclomatic manganese tricarbonyl compounds which may be employed
in the compositions of the present application include, for example, cyclopentadienyl
manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese
tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl. Yet other examples of
suitable cyclomatic manganese tricarbonyl compounds are disclosed in
U.S. Pat. No. 5,575,823 and
U.S. Pat. No. 3,015,668 both of which disclosures are herein incorporated by reference in their entirety.
[0062] Other commercially available detergents may be used in combination with the reaction
products described herein. Such detergents include but are not limited to succinimides,
Mannich base detergents, PIB amine, quaternary ammonium detergents, bis-aminotriazole
detergents as generally described in
U.S. patent application Ser. No. 13/450,638, and a reaction product of a hydrocarbyl substituted dicarboxylic acid, or anhydride
and an aminoguanidine, wherein the reaction product has less than one equivalent of
amino triazole group per molecule as generally described in
U.S. patent application Ser. Nos. 13/240,233 and
13/454,697.
[0063] The additives of the present application and optional additives used in formulating
the fuels of this invention may be blended into the base fuel individually or in various
subcombinations. In some embodiments, the additive components of the present application
may be blended into the fuel concurrently using an additive concentrate, as this takes
advantage of the mutual compatibility and convenience afforded by the combination
of ingredients when in the form of an additive concentrate. Also, use of a concentrate
may reduce blending time and lessen the possibility of blending errors.
Fuels
[0064] The fuels of the present application may be applicable to the operation of diesel,
jet, or gasoline engines, and preferably, spark-ignition or gasoline engines. The
engines may include both stationary engines (e.g., engines used in electrical power
generation installations, in pumping stations, etc.) and ambulatory engines (e.g.,
engines used as prime movers in automobiles, trucks, road-grading equipment, military
vehicles, etc.). For example, the fuels may include any and all middle distillate
fuels, diesel fuels, biorenewable fuels, biodiesel fuel, fatty acid alkyl ester, gas-to-liquid
(GTL) fuels, gasoline, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic
fuels, such as Fischer-Tropsch fuels, liquid petroleum gas, bunker oils, coal to liquid
(CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from
coal (natural, cleaned, and petcoke), genetically engineered biofuels and crops and
extracts therefrom, and natural gas. Preferably, the additives herein are used in
spark-ignition fuels or gasoline. "Biorenewable fuels" as used herein is understood
to mean any fuel which is derived from resources other than petroleum. Such resources
include, but are not limited to, corn, maize, soybeans and other crops; grasses, such
as switchgrass, miscanthus, and hybrid grasses; algae, seaweed, vegetable oils; natural
fats; and mixtures thereof. In an aspect, the biorenewable fuel can comprise monohydroxy
alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples
of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol,
t-butyl alcohol, amyl alcohol, and isoamyl alcohol. Preferred fuels include diesel
fuels.
[0065] Accordingly, aspects of the present application are directed to methods of or the
use of the noted fuel additive package for controlling or reducing fuel injector deposits,
controlling or reducing intake valve deposits, controlling or reducing combustion
chamber deposits, and/or controlling or reducing intake valve sticking in one of port-injection
engines, direct-injection engines, and preferably both engine types. In some aspects,
the method may also comprise mixing into the fuel at least one of the optional additional
ingredients described above. The improved engine performance may be evaluated pursuant
to the test protocols of ASTM D6201 or by the methods as set forth in the following
two SAE publications:
Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct
Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi:10.4271/2013-01-2616 and/or
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, both of which are incorporated herein by reference. Intake valve sticking may be
evaluated using the test protocols at Southwest Research Institute (SWRI, San Antonio
Texas) or similar test house.
[0066] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used
in its ordinary sense, which is well-known to those skilled in the art. Specifically,
it refers to a group having a carbon atom directly attached to the remainder of the
molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group
is independently selected from hydrocarbon substituents, and substituted hydrocarbon
substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups,
mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl
groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon
substituents are present for every ten carbon atoms in the hydrocarbyl group.
[0067] As used herein, the term "percent by weight" or "wt%", unless expressly stated otherwise,
means the percentage the recited component represents to the weight of the entire
composition. All percent numbers herein, unless specified otherwise, is weight percent.
[0068] The term "alkyl" as employed herein refers to straight, branched, cyclic, and/or
substituted saturated chain moieties from about 1 to about 200 carbon atoms. The term
"alkenyl" as employed herein refers to straight, branched, cyclic, and/or substituted
unsaturated chain moieties from about 3 to about 30 carbon atoms. The term "aryl"
as employed herein refers to single and multi-ring aromatic compounds that may include
alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms
including, but not limited to, nitrogen, and oxygen.
[0069] As used herein, the molecular weight is determined by gel permeation chromatography
(GPC) using commercially available polystyrene standards (with a Mp of about 162 to
about 14,000 as the calibration reference). The molecular weight (Mn) for any embodiment
herein may be determined with a gel permeation chromatography (GPC) instrument obtained
from Waters or the like instrument and the data 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 300×7.5 mm; particle size of 5 µ, and pore size ranging from 100-10000 Å) with
the column temperature at about 40 °C. Un-stabilized HPLC grade tetrahydrofuran (THF)
may be used as solvent, at a flow rate of 0.38 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 weight percent and used
without filtration. GPC measurements are also described in
US 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.
[0070] It is to be understood that throughout the present disclosure, the terms "comprises,"
"includes," "contains," etc. are considered open-ended and include any element, step,
or ingredient not explicitly listed. The phrase "consists essentially of" is meant
to include any expressly listed element, step, or ingredient and any additional elements,
steps, or ingredients that do not materially affect the basic and novel aspects of
the invention. The present disclosure also contemplates that any composition described
using the terms, "comprises," "includes," "contains," is also to be interpreted as
including a disclosure of the same composition "consisting essentially of" or "consisting
of" the specifically listed components thereof.
EXAMPLES
[0071] The following examples are illustrative of exemplary embodiments of the disclosure.
In these examples as well as elsewhere in this application, all ratios, parts, and
percentages are by weight unless otherwise indicated. It is intended that these examples
are being presented for the purpose of illustration only and are not intended to limit
the scope of the invention disclosed herein. The specifications for base fuels A,
B, and C used in the Examples are shown below in Table 1.
Table 1: Fuel Specifications.
FUEL PROPERTY |
BASE FUEL A |
BASE FUEL B |
BASE FUEL C |
API Gravity |
60.3 |
58.5 |
58.7 |
Specific Gravity |
0.7377 |
0.7447 |
0.7440 |
Density |
0.7370 |
0.7440 |
0.7432 |
% Benzene |
0.47 |
<0.10 |
n.a. |
Bromine No. |
9.7 |
<0.5 |
n.a. |
BTU Gross (btu/lb) |
18711 |
19614 |
19674 |
BTU Net (btu/lb) |
17477 |
18409 |
18465 |
Unwashed Gum (ASTM D-381) |
3 |
3.5 |
1.5 |
Washed Gum (ASTM D-381) |
<0.5 |
<0.5 |
<0.5 |
ASTM D-525 Oxidation (minutes) |
960 |
960+ |
960+ |
RVP (ASTM D-5191) |
9.46 |
8.76 |
8.8 |
%Carbon |
82.63 |
86.79 |
n.a. |
%Hydrogen |
13.53 |
13.21 |
n.a. |
Aromatics (vol-%) |
27.9 |
29.1 |
30.7 |
Olefins (vol-%) |
4.7 |
1.2 |
9.2 |
Saturates (vol-%) |
67.4 |
69.7 |
60.1 |
Ethanol (vol-%) |
9.3 |
<0.10 |
n.a. |
Oxygen Content |
3.84 |
<0.02 |
0 |
Sulfur (ppm) |
8.4 |
30 |
4.6 |
RON |
98.2 |
97.4 |
91.4 |
MON |
87.5 |
89 |
83.3 |
Octane (R+M)/2 |
92.85 |
93.2 |
87.35 |
ASTM D-86 (Temperature °F) |
Initial Boiling Point |
87 |
84.6 |
91.3 |
5% |
99.9 |
108 |
113.7 |
10% |
110.5 |
121.5 |
125 |
20% |
125.2 |
104.6 |
140.2 |
30% |
140.3 |
163 |
157.1 |
40% |
152.5 |
191.4 |
174.2 |
50% |
165.6 |
215.8 |
193.3 |
60% |
228.4 |
228.4 |
227.1 |
70% |
250.5 |
237.3 |
257.8 |
80% |
276 |
254 |
288.5 |
90% |
316 |
337.5 |
332.6 |
95% |
343.6 |
338.4 |
368.4 |
End Point |
398.5 |
398.7 |
423.8 |
% Recovery |
96.1 |
97.3 |
97.2 |
Residue |
1.1 |
1.1 |
1.1 |
Loss |
2.8 |
1.6 |
1.7 |
EXAMPLE 1
[0072] An oleylamidopropyl dimethylammonium betaine quaternary ammonium internal salt can
be made by the process described in
US Patent No. 8,894,726 (Inventive Example 3), which is incorporated herein by reference.
EXAMPLE 2
[0073] Inventive and comparative fuel additive packages of Table 2 below were prepared.
The Mannich product was prepared from a high reactivity polyisobutylene cresol, dibutylamine,
and formaldehyde according to a known method (see, e.g.,
US 6,800,103, which is incorporated herein by reference); the quaternary ammonium internal salt
was oleylamidopropyl dimethylammonium from Example 1; the propoxylated alcohol was
a blend of commercially available C16-C18 propoxylated alcohols; and the succinimide
detergent was a 950 number average molecular weight polyisobutenyl mono-succinimide
derived from tetraethylene pentaamine (TEPA).
Table 2
Ingredients |
Inventive 1 |
Inventive 2 |
ppmw |
ppmw |
Mannich Detergent |
82.4 |
82.4 |
Quaternary Ammonium Internal Salt |
2.0 |
2.0 |
Propoxylated alcohol |
33.1 |
41.2 |
Mono-Succinimide |
3.1 |
3.1 |
Propoxylated alcohol to Mannich detergent weight ratio |
0.40:1 |
0.50:1 |
Mannich detergent to Quaternary ammonium salt weight ratio |
41.2:1 |
41.2:1 |
* The additive package also contained other non-detergent ingredients, such as demulsifier
and solvent. |
[0074] The additive packages of Table 2 were blended into Base Fuel A at the treat rates
set forth in Table 3 below. The fuel was then evaluated for intake valve deposits
and improvements from the base fuel without the additive determined pursuant to ASTM
D6201.
Table 3
IVD testing |
Base Fuel |
Inventive 1 |
Inventive 2 |
|
|
|
ASTM D6201, IVD, mg |
1263.1 |
62.7 |
53.9 |
improvement from Base Fuel A IVD, % |
- |
95.0 |
95.7 |
[0075] As shown in Table 3 above, the inventive samples exhibited good IVD results.
EXAMPLE 3
[0076] The fuel additives of Example 2 where further evaluated in an additive package of
Table 4 below. The additives were the same as Example 2 except Inventive 4 included
a bis-succinimide instead of a mono-succinimide as noted in Table 4.
Table 4
Ingredients |
Comparative 1 |
Inventive 3 |
Inventive 4 |
ppmw |
ppmw |
ppmw |
Mannich Detergent |
164.1 |
164 |
164 |
Quaternary Ammonium Internal Salt |
|
2.3 |
2.3 |
Propoxylated alcohol |
49.2 |
49.2 |
49.2 |
Mono-Succinimide |
5.6 |
5.6 |
|
Bis-Succinimide |
|
|
7.1 |
Propoxylated alcohol to Mannich detergent weight ratio |
0.30/1 |
0.30/1 |
0.30/1 |
Mannich detergent to Quaternary ammonium salt weight ratio |
-- |
71.3: 1 |
71.3: 1 |
* The additive package also contained other non-detergent ingredients, such as demulsifier
and solvent. |
[0077] A series of tests were run to evaluate the impact that the additive packages have
on fuel inject deposits in a gasoline direct injection engine (GDI). All tests were
run with a consistent Base Fuel B during a Dirty-up (DU), Clean-up (CU) and/or Keep
Clean (KC) phases of the respective test. The additive packages of Table 4 above were
tested to evaluate the ability of each fuel additive to improve injector performance
by reducing injector deposits in the GDI engine.
[0078] Each base fuel was investigated for a DU level by indirect measurements of injector
fouling, such as by pulse width or long term fuel trim (LTFT), on a gasoline direct
injection GM LHU engine pursuant to the RIFT methods as set forth in
Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct
Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi:10.4271/2013-01-2616 and/or
Shanahan, C., Smith, S., and/or 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, both of which are incorporated by reference herein.
[0079] In order to accelerate the DU phase of the Base Fuel, a combination of di-tert-butyl
disulfide (DTBDS 406.1ppmw) and tert-butyl hydrogen peroxide (TBHP, 286ppmw) were
added to the base fuel and the DU was accelerated to provide the fouling in the range
of 5-12%. Percent of fouling is calculated as:
[0080] GDI CU deposit tests were conducted to demonstrate the removal of deposits that had
been formed in the fuel injectors during the dirty-up (DU) phase. The Additive packages
of Table 4 were blended into the Base Fuel B that was used for DU. The test procedure
consists of a 114 hour cycle at 2000 rpm and 100 Nm torque with continuous monitoring
of injection pulse width to maintain stoichiometric Air/Fuel ratio on the GM LHU engine.
After 66 hours of test operation, the fuel was changed to an additized formulation
that is designed to have a clean-up effect. The percentage of injector pulse width
increase, and subsequent decrease, after completion of the 114 hour cycle is one parameter
for evaluating the fouling or cleaning effect of the fuel candidate at the treat rates
set forth in Table 5 below, which demonstrated a clean-up (CU) of over 100% within
48 hours. CU is calculated as in the following equation:
Table 5
|
Comparative 1 |
Inventive 3 |
Inventive 4 |
Mannich, ppmw |
164.1 |
164.0 |
164.0 |
Quaternary ammonium salt, ppmw |
0 |
2.3 |
2.3 |
GDI CU by RIFT method, % |
79.9 |
100.09 |
101.9 |
[0081] As shown in Table 5 above, the inventive examples exhibited improved injector clean-up
relative to the comparative example. Furthermore, GDI keep-clean (KC) was demonstrated
by using the additive package of Table 1 in the base fuel at a certain treat rate
on a GM LHU engine. The duration of the KC phase was 66 hours. In the KC phase, it
can be seen that the additive package of Inventive 1 prevented deposits from being
formed in the fuel as shown in Figure 1. Once the additive is added, the LTFT decreased
from about 0.78% to about -3.14% as shown in Figure 2.
[0082] GDI CU deposit tests in Table 6 were carried out on a 2008 Pontiac Solstice vehicle.
The additive packages were blended into Base Fuel C. The DU procedure was running
by RTFT method described previously between 2000-3000 miles to achieve delta LTFT
(Δ = end of DU-beginning of DU) of about 6.0% or above. At the end of DU, the fuel
was changed to an additized formulation that is designed to have a clean-up effect
Table 6
Composition |
Inventive 5 |
Comparative 2 |
Comparative 3 |
ppmw |
ppmw |
ppmw |
Mannich Detergent |
79.6 |
0 |
79.6 |
Quaternary Ammonium Internal Salt |
2.9 |
2.9 |
0 |
Propoxylated alcohol |
23.9 |
23.9 |
23.9 |
LTFT in the beginning of DU, % |
-3.1 |
-3.9 |
-5.5 |
LTFT at the end of DU, % |
4.7 |
6.3 |
5.5 |
LTFT at the end of CU, % |
0.8 |
7.8 |
3.9 |
GDI CU, % |
50.0 |
-14.7 |
14.5 |
[0083] With combination of Mannich and Quaternary ammonium salt, the CU% is 50% while Mannich
alone provided 14.5% GDI CU and quaternary ammonium salt -14.7% (continuing DU) as
shown in FIG. 3.
[0084] It is noted that, as used in this specification and the appended claims, the singular
forms "a," "an," and "the," include plural referents unless expressly and unequivocally
limited to one referent. Thus, for example, reference to "an antioxidant" includes
two or more different antioxidants. As used herein, the term "include" and its grammatical
variants are intended to be non-limiting, such that recitation of items in a list
is not to the exclusion of other like items that can be substituted or added to the
listed items
[0085] For the purposes of this specification and appended claims, unless otherwise indicated,
all numbers expressing quantities, percentages or proportions, and other numerical
values used in the specification and claims, are to be understood as being modified
in all instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification and attached claims
are approximations that can 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.
[0086] 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.
[0087] 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.
[0088] 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.
That is, it is also further understood that any range between the endpoint values
within the broad 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.
[0089] 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.
[0090] The invention also relates to the following numbered embodiments:
- 1. A fuel additive package for a spark-ignition engine comprising:
a Mannich detergent including the reaction product of a hydrocarbyl-substituted phenol,
one or more aldehydes, and one or more amines; and
a quaternary ammonium internal salt obtained from amines or polyamines that is substantially
devoid of any free anion species.
- 2. The fuel additive package of embodiment 1, further comprising an alkoxylated alcohol.
- 3. The fuel additive package of embodiment 2, wherein a weight ratio of the alkoxylated
alcohol to the Mannich detergent is about 0.8 or less.
- 4. The fuel additive package of embodiment 3, wherein the alkoxylated alcohol is a
polyether prepared by reacting an alkyl alcohol or an alkylphenol with an alkylene
oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof,
or combinations thereof.
- 5. The fuel additive package of embodiment 1, wherein a weight ratio of the Mannich
detergent to the quaternary ammonium internal salt is about 5:1 to about 100:1.
- 6. The fuel additive package of embodiment 1, wherein the Mannich detergent has the
structure of Formula I:
wherein R1 is hydrogen or a C1 to C4 alkyl group, R2 is a hydrocarbyl group having a number average molecular weight of about 500 to about
3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are, independently, hydrogen, a C1 to C12 alkyl group, or a C1 to C4 alkyl amino
C1-C12 alkyl group.
- 7. The fuel additive package of embodiment 1, wherein the quaternary ammonium internal
salt has the structure of Formula II
wherein R and R' are, independently, alkylene linkers having 1 to 10 carbon atoms;
R8 is a C12 to C100 alkylene, alkene, or hydrocarbyl group or an aryl group or optionally
substituted aryl group; each R9 is, independently, a linear or branched C1 to C4 alkyl group; and R10 is a hydrogen atom or a C1 to C4 alkyl group.
- 8. The fuel additive package of embodiment 2, wherein the alkoxylated alcohol is a
polyether having the structure of Formula III:
wherein R6 is an aryl group or a linear, branched, or cyclic aliphatic group having 5 to 50
carbons, R7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100.
- 9. The fuel additive package of embodiment 2, wherein the fuel additive package includes
about 20 to about 60 weight percent of the Mannich detergent, about 1 to about 15
weight percent of the quaternary ammonium internal salt, and about 5 to about 30 weight
percent of the alkoxylated alcohol.
- 10. The fuel additive package of embodiment 2, further comprising a succinimide detergent
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.
- 11. The fuel additive package of embodiment 9, wherein the fuel additive package includes
about 0.1 to about 10 weight percent of the succinimide detergent.
- 12. The fuel additive package of embodiment 11, wherein the succinimide detergent
is a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted
bis-succinimide detergent, or a combination thereof.
- 13. The fuel additive package of embodiment 11, further comprising one or more of
a demulsifier, a corrosion inhibitor, an antiwear additive, an antioxidant, a metal
deactivator, an antistatic additive, a dehazer, an antiknock additive, a lubricity
additive, and/or a combustion improver.
- 14. A gasoline fuel composition comprising about 15 to about 300 ppmw of a Mannich
detergent including the reaction product of a hydrocarbyl-substituted phenol, one
or more aldehydes, and one or more amines;
about 0.1 to about 20 ppmw of a quaternary ammonium internal salt obtained from amines
or polyamines that is substantially devoid of any free anion species; and
about 5 to about 150 ppmw of an alkoxylated alcohol.
- 15. A method of improving the injector performance of a gasoline direct injection
(GDI) engine, the method comprising:
operating the gasoline direct injection engine on a fuel composition containing a
major amount of a gasoline fuel and a minor amount of the fuel additive package of
claim 1; and
wherein the fuel additive package in the gasoline fuel improves the injector performance
of the gasoline direct injection engine.
- 16. The method of embodiment 15, wherein the improved injector performance is one
of improved fuel flow, improved fuel economy, improved engine efficiency, or combinations
thereof.
- 17. The method of embodiment 16, wherein the improved injector performance is measured
by one of injector pulse width, injection duration, injector flow, or combinations
thereof.