U.S. patent application number 16/402989 was filed with the patent office on 2019-12-19 for quaternary ammonium fuel additives.
The applicant listed for this patent is Afton Chemical Corporation. Invention is credited to Scott D. Schwab.
Application Number | 20190382674 16/402989 |
Document ID | / |
Family ID | 66673312 |
Filed Date | 2019-12-19 |
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United States Patent
Application |
20190382674 |
Kind Code |
A1 |
Schwab; Scott D. |
December 19, 2019 |
QUATERNARY AMMONIUM FUEL ADDITIVES
Abstract
The present disclosure provides fuel additives including a
quaternary ammonium salt formed by reacting an alkyl carboxylate
with a compound formed from a hydrocarbyl substituted acylating
agent reacted with a select amine. Also provided herein are fuel
compositions including the novel fuel additives and methods of
combusting a fuel including the fuel additives herein. The unique
quaternary ammonium salts herein are advantageous because they can
be made through a simple alkylation process and provide improved
detergency at low treat rates by making available a relatively less
sterically hindered quaternary nitrogen for detergency activity in
the fuel.
Inventors: |
Schwab; Scott D.; (Richmond,
VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Afton Chemical Corporation |
Richmond |
VA |
US |
|
|
Family ID: |
66673312 |
Appl. No.: |
16/402989 |
Filed: |
May 3, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16009403 |
Jun 15, 2018 |
10308888 |
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16402989 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 1/1883 20130101;
C10L 10/04 20130101; C10L 2200/0259 20130101; C10L 2270/026
20130101; C10L 1/224 20130101; F02M 65/008 20130101; C10L 10/06
20130101; C10L 1/2383 20130101; C10L 1/232 20130101; C10L 2270/023
20130101; C10L 1/2222 20130101; F02M 25/00 20130101; F02M 25/10
20130101; C10L 1/189 20130101 |
International
Class: |
C10L 10/04 20060101
C10L010/04; C10L 10/06 20060101 C10L010/06; F02M 65/00 20060101
F02M065/00; C10L 1/222 20060101 C10L001/222; C10L 1/232 20060101
C10L001/232 |
Claims
1. A fuel additive comprising a quaternary ammonium salt formed by
the reaction of an alkyl carboxylate with a compound obtained by
reacting a hydrocarbyl substituted acylating agent and an amine,
wherein the amine has the structure ##STR00011## wherein A is a
hydrocarbyl linker with 2 to 10 carbon units and including one or
more carbon units thereof independently replaced with a bivalent
moiety selected from the group consisting of --O--, --N(R')--,
--C(O)--, --C(O)O--, --C(O)NR'; R.sub.1 and R.sub.2 are
independently alkyl groups containing 1 to 8 carbon atoms; and R'
is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl.
2. The fuel additive of claim 1, wherein the alkyl carboxylate is
alkyl oxalate, alkyl salicylate, or a combination thereof.
3. The fuel additive of claim 1, wherein the alkyl group in the
alkyl carboxylate is C1 to C6 alkyl.
4. The fuel additive of claim 1, wherein A is
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being 1, 2, 3, or 4 and X being O or NR''
with R'' being hydrogen or a hydrocarbyl group.
5. The fuel additive of claim 4, wherein X is oxygen
6. The fuel additive of claim 1, wherein the amine is selected from
3-(2-(dimethyl amino)ethoxy)propylamine,
N,N-dimethyldipropylenetriamine, and mixtures thereof.
7. The fuel additive of claim 1, wherein the hydrocarbyl substitued
acylating agent is selected from a hydrocarbyl substituted
dicarboxylic acid or anhydride derivative thereof, a fatty acid, or
mixtures thereof.
8. The fuel additive of claim 1, wherein the hydrocarbyl
substituent has a number average molecular weight of about 200 to
about 2500 as measured by GPC using polystyrene as a calibration
reference.
9. A fuel composition comprising a major amount of a fuel and a
minor amount of a quaternary ammonium salt formed by the reaction
of an alkyl carboxylate with a compound obtained by reacting a
hydrocarbyl substituted acylating agent and an amine, wherein the
formed quaternary ammonium salt has the structure ##STR00012##
wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, --C(O)NR'; R.sub.1, R.sub.2, and
R.sub.3 are independently alkyl groups containing 1 to 8 carbon
atoms; and R' is independently a hydrogen or a group selected from
C.sub.1-6 aliphatic, phenyl, or alkylphenyl; and R.sub.4 and
R.sub.5 are independently selected from a hydrogen, an acyl group,
or a hydrocarbyl substituted acyl group, wherein if one of R.sub.4
or R.sub.5 is hydrogen, then the other of R.sub.4 and R.sub.5 is
the acyl group or the hydrocarbyl substituted acyl group, if both
R.sub.4 and R.sub.5 include carbonyl moieties, then one of R.sub.4
and R.sub.5 includes the acyl group and the other of R.sub.4 and
R.sub.5 includes the hydrocarbyl substitued acyl group, and R.sub.4
and R.sub.5 together with the N atom to which they are attached,
combine to form a ring moiety; and M.sup.- is a carboxylate.
10. The fuel composition of claim 9, comprising about 1 to about
100 ppm of the quaternary ammonium salt.
11. The fuel composition of claim 9, wherein the carboxylate is
oxalate, salicylate, or combinations thereof.
12. The fuel composition of claim 9, wherein A is
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being 1, 2, 3, or 4 and X being O or NR''
with R'' being hydrogen or a hydrocarbyl group.
13. The fuel composition of claim 12, wherein X is oxygen.
14. The fuel composition of claim 12, wherein A includes a moiety
derived from 3-(2-(dimethylamino)ethoxy)propylamine,
N,N-dimethyldipropylenetriamine, or mixtures thereof.
15. The fuel composition of claim 9, wherein R.sub.4 and R.sub.5,
together with the nitrogen atom to which they are attached, combine
to form a hydrocarbyl substituted succinimide.
16. The fuel composition of claim 15, wherein the hydrocarbyl
substituent has a number average molecular weight of about 200 to
about 2500 as measured by GPC using polystyrene as a calibration
reference.
17. The fuel composition of claim 9, wherein the hydrocarbyl
substituent of R.sub.4 or R.sub.5 has a number average molecular
weight of about 200 to about 2500 as measured by GPC using
polystyrene as a calibration reference.
18. A method of operating a fuel injected engine to provide
improved engine performance, the method comprising combusting in
the engine a fuel composition including a major amount of fuel and
about 1 to about 100 ppm of a quaternary ammonium salt formed by
the reaction of an alkyl carboxylate with a compound obtained by
reacting a hydrocarbyl substituted acylating agent and an amine,
wherein the amine has the structure ##STR00013## wherein A is a
hydrocarbyl linker with 2 to 10 carbon units and including one or
more carbon units thereof independently replaced with a bivalent
moiety selected from the group consisting of --O--, --N(R')--,
--C(O)--, --C(O)O--, --C(O)NR'; R.sub.1 and R.sub.2 are
independently alkyl groups containing 1 to 8 carbon atoms; and R'
is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl.
19. The method of claim 18, wherein the improved engine performance
is an average flow loss of about 45 percent or less when measured
according to a CEC F-23-01 (XUD-9) test.
20. A method of claim 18, wherein the formed quaternary ammonium
salt has the structure ##STR00014## wherein A includes 2 to 6
carbon units with one carbon unit thereof independently replaced
with --O-- or --NH--; R.sub.1, R.sub.2, and R.sub.3 are
independently alkyl groups containing 1 to 8 carbon atoms; and
R.sub.4 and R.sub.5 are independently selected from a hydrogen, an
acyl group, or a hydrocarbyl substituted acyl group, wherein if one
of R.sub.4 or R.sub.5 is hydrogen, then the other of R.sub.4 and
R.sub.5 is the acyl group or the hydrocarbyl substituted acyl
group, if both R.sub.4 and R.sub.5 include carbonyl moieties, then
one of R.sub.4 and R.sub.5 includes the acyl group and the other of
R.sub.4 and R.sub.5 includes the hydrocarbyl substitued acyl group,
and R.sub.4 and R.sub.5 together with the N atom to which they are
attached, combine to form a ring moiety; and M.sup.- is a
carboxylate.
21. The method of claim 20, wherein the carboxylate includes
oxalate, salicylate, or combinations thereof.
22. The method of claim 20, wherein the hydrocarbyl substituent has
a number average molecular weight of about 200 to about 2500 as
measured by GPC using polystyrene as a calibration reference.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. application Ser.
No. 16/009,403 filed Jun. 15, 2018, which is hereby incorporated by
reference in its entirety.
TECHNICAL FIELD
[0002] This disclosure is directed to fuel additive compositions
that include hydrocarbyl soluble quaternary ammonium salts and to
methods for using the salts in a fuel composition as fuel
detergents.
BACKGROUND
[0003] 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. 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.
[0004] 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, but at the same time be detrimental to another
characteristic of the fuel. Other fuel additives often require an
unreasonably high treat rate to achieve their desired effect, which
tends to place undesirable limits on the available amounts of other
additives in the fuel composition.
[0005] Quaternary ammonium compounds, such as alkoxylated salts,
have recently been developed as detergents for fuels. The
quaternary ammonium compounds, in some instances, are obtained from
an acylating agent reacted with a polyamine, which is then
alkylated or quaternized by a quaternizing agent. While providing
improved detergency compared to prior detergents, these quaternary
ammonium compounds and their methods of alkylation, however, still
have several shortcomings. For example, in some instances, ethylene
oxides and propylene oxides are used to make such detergents. Such
oxides, however, are often undesired due to their handling
difficulties. Quaternary ammonium compounds may also be formed
through alkylation using dialkyl carbonates. However, the carbonate
anion may be susceptible to precipitation and drop out of certain
types of fuels or fuel additive packages. Other quaternary ammonium
salts require halogenated carboxylic acids as quaternary agents.
These salts may include residual halogens that may be less
preferred in some applications. In yet other instances, removing
undesirable ash generating components from the quaternizing
manufacturing process is complicated.
[0006] While offering an improvement in detergency, prior
quaternary ammonium compounds still have limitations in that
relatively higher treat rates may be required to achieve adequate
detergency effect in some applications. Often the pendant
quaternary nitrogen in the quaternary ammonium salt is a derived
from a diamine, such as dimethylamino propylamine, a common
tertiary diamine obtained from the Michael reaction between
dimethylamine and acrylonitrile through a subsequent hydrogenation.
This diamine is a commonly available and convenient amine to form a
quaternary ammonium salt. However, when using such tertiary amine
source in a quaternizing reaction, it is often hindered in its
availability for alkylation and/or activity as a detergent. As a
result, quaternary ammonium salts obtained from such tertiary
amines may not be sufficiently effective for improving injector
performance at relatively low treat rates.
SUMMARY
[0007] In one aspect, a fuel additive is provided that includes a
quaternary ammonium salt formed by the reaction of an alkyl
carboxylate with an amide or imide compound obtained by reacting a
hydrocarbyl substituted acylating agent and an amine, wherein the
amine has the structure of Formula I
##STR00001##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, --C(O)NR'; R.sub.1 and R.sub.2 are
independently alkyl groups containing 1 to 8 carbon atoms; and R'
is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl.
[0008] The fuel additive of the preceding paragraph may be combined
with one or more optional features either individually or in any
combination thereof. These optional features include: wherein the
alkyl carboxylate is alkyl oxalate, alkyl salicylate, or a
combination thereof; and/or wherein the alkyl group in the alkyl
carboxylate is C.sub.1 to C.sub.6 alkyl; and/or wherein A is
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being 1, 2, 3, or 4 and X being oxygen or
NR'' with R'' being hydrogen or a hydrocarbyl group; and/or wherein
X is oxygen; and/or wherein the amine is selected from
3-(2-(dimethylamino)ethoxy)propylamine, N,N-dimethyl dipropylene
triamine, and mixtures thereof; and/or wherein the hydrocarbyl
substitued acylating agent is selected from a hydrocarbyl
substituted dicarboxylic acid or anhydride derivative thereof, a
fatty acid, or mixtures thereof; and/or wherein the hydrocarbyl
substituent has a number average molecular weight of about 200 to
about 2500 as measured by GPC using polystyrene as a calibration
reference.
[0009] In another aspect, the present disclosure provides a fuel
composition comprising a major amount of a fuel and a minor amount
of, in one aspect, a quaternary ammonium salt formed by the
reaction of an alkyl carboxylate with an amide or imide compound
obtained by reacting a hydrocarbyl substituted acylating agent and
an amine of Formula I above. In another aspect, the fuel
composition includes the formed quaternary ammonium salt of the
structure of Formula II
##STR00002##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, or --C(O)NR'; R.sub.1, R.sub.2, and
R.sub.3 are independently alkyl groups containing 1 to 8 carbon
atoms; and R' is independently a hydrogen or a group selected from
C.sub.1-6 aliphatic, phenyl, or alkylphenyl; and R.sub.4 and
R.sub.5 are independently a hydrogen, an acyl group, or a
hydrocarbyl substituted acyl group, wherein if one of R.sub.4 or
R.sub.5 is hydrogen, then the other of R.sub.4 and R.sub.5 is the
acyl group or the hydrocarbyl substituted acyl group, and if both
R.sub.4 and R.sub.5 include carbonyl moieties, then one of R.sub.4
and R.sub.5 includes the acyl group and the other of R.sub.4 and
R.sub.5 includes the hydrocarbyl substitued acyl group, and R.sub.4
and R.sub.5 together with the N atom to which they are attached,
combine to form a ring moiety; and M.sup.- is a carboxylate.
[0010] The fuel additive of the preceding paragraph may be combined
with one or more optional features either individually or in any
combination thereof. These optional features include: wherein the
fuel composition includes about 1 to about 100 ppm of the
quaternary ammonium salt; and/or wherein the carboxylate is
oxalate, salicylate, or combinations thereof; and/or wherein A is
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being 1, 2, 3, or 4 and X being oxygen or
NR'' with R'' being hydrogen or a hydrocarbyl group; and/or wherein
X is oxygen; and/or wherein A includes a moiety derived from
3-(2-(dimethylamino)ethoxy) propylamine,
N,N-dimethyldipropylenetriamine, or mixtures thereof; and/or
wherein R.sub.4 and R.sub.5, together with the nitrogen atom to
which they are attached, combine to form a hydrocarbyl substituted
succinimide; and/or wherein the hydrocarbyl substituent has a
number average molecular weight of about 200 to about 2500 as
measured by GPC using polystyrene as a calibration reference;
and/or wherein the hydrocarbyl substituent of R.sub.4 or R.sub.5
has a number average molecular weight of about 200 to about 2500 as
measured by GPC using polystyrene as a calibration reference.
[0011] In yet a further aspect, the present disclosure provides a
method of operating a fuel injected engine to provide improved
engine performance, such as but not limited to, reducing injector
deposits in an internal combustion engine or fuel system for an
internal combustion engine, cleaning-up fouled injectors, or
un-sticking injectors. The methods herein include combusting in the
engine a fuel composition including a major amount of fuel and
about 1 to about 100 ppm of a quaternary ammonium salt formed by
the reaction of an alkyl carboxylate with an amide or imide
compound obtained by reacting a hydrocarbyl substituted acylating
agent and an amine, wherein the amine has the structure
##STR00003##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, or --C(O)NR'; R.sub.1 and R.sub.2
are independently alkyl groups containing 1 to 8 carbon atoms; and
R' is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl. The present disclosure also
provides for the use of the above described quaternary ammonium
salt for providing improved engine performance, such as but not
limited to, reducing injector deposits in an internal combustion
engine or fuel system for an internal combustion engine,
cleaning-up fouled injectors, or un-sticking injectors.
[0012] The methods or use described in the preceding paragraph may
be combined with one or more optional features either individually
or in any combination thereof. These optional features include:
wherein the improved engine performance is an average flow loss of
about 45 percent or less when measured according to a CEC F-23-01
(XUD-9) test; and/or wherein the formed quaternary ammonium salt
has the structure
##STR00004##
Wherein A includes 2 to 6 carbon units with one carbon unit thereof
independently replaced with --O-- or --NH--; and/or wherein
R.sub.1, R.sub.2, and R.sub.3 are independently alkyl groups
containing 1 to 8 carbon atoms; and/or wherein R.sub.4 and R.sub.5
are independently a hydrogen, an acyl group, or a hydrocarbyl
substituted acyl group; and/or wherein if one of R.sub.4 or R.sub.5
is hydrogen, then the other of R.sub.4 and R.sub.5 is the acyl
group or the hydrocarbyl substituted acyl group, and if both
R.sub.4 and R.sub.5 include carbonyl moieties, then one of R.sub.4
and R.sub.5 includes the acyl group and the other of R.sub.4 and
R.sub.5 includes the hydrocarbyl substitued acyl group, and R.sub.4
and R.sub.5 together with the N atom to which they are attached,
combine to form a ring moiety; and/or wherein M.sup.- is a
carboxylate; and/or wherein the carboxylate is oxalate, salicylate,
or combinations thereof; and/or wherein the hydrocarbyl substituent
has a number average molecular weight of about 200 to about 2500 as
measured by GPC using polystyrene as a calibration reference;
and/or wherein A is
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being 1, 2, 3, or 4 and X being oxygen or
NR'' with R'' being hydrogen or a hydrocarbyl group; and/or wherein
X is oxygen.
DETAILED DESCRIPTION
[0013] The present disclosure provides fuel additives including a
quaternary ammonium salt formed by reacting an alkyl carboxylate
with an amide or imide compound formed by reacting a hydrocarbyl
substituted acylating agent with a select amine. Also provided
herein are fuel compositions including the novel fuel additives and
methods of combusting a fuel including the fuel additives herein.
The unique quaternary ammonium salts herein are beneficial because
they can be made through a simple alkylation process and provide
improved detergency at low treat rates by making available a
relatively less sterically hindered quaternary nitrogen for
detergent activity in the fuel.
[0014] In one aspect of this disclosure, an exemplary fuel additive
including a quaternary ammonium salt may be formed through a
reaction between an alkyl carboxylate and an amide or imide
compound obtained by reacting a hydrocarbyl substituted acylating
agent and an amine. In one approach of this aspect, the amine has
the structure of Formula I
##STR00005##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, and --C(O)NR'. R.sub.1 and R.sub.2
are independently alkyl groups containing 1 to 8 carbon atoms, and
R' is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl. In another approach of this
aspect, the formed quaternary ammonium salt may be that of Formula
II discussed below.
[0015] In another aspect of this disclosure, a fuel composition is
provided including a major amount of a fuel and a minor amount of a
quaternary ammonium salt formed by the reaction of an alkyl
carboxylate with an amide or imide compound obtained by reacting a
hydrocarbyl substituted acylating agent and an amine, which may be
the amine of Formula I above. In one approach of this aspect, the
formed quaternary ammonium salt has the structure of Formula II
##STR00006##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, and --C(O)NR'. R.sub.1, R.sub.2,
and R.sub.3 are independently alkyl groups containing 1 to 8 carbon
atoms; and R' is independently a hydrogen or a group selected from
C.sub.1-6 aliphatic, phenyl, or alkylphenyl. R.sub.4 and R.sub.5
are independently a hydrogen, an acyl group, or a hydrocarbyl
substituted acyl group. If one of R.sub.4 or R.sub.5 is hydrogen,
then the other of R.sub.4 and R.sub.5 is the acyl group or the
hydrocarbyl substituted acyl group. If both R.sub.4 and R.sub.5
include carbonyl moieties, then one of R.sub.4 and R.sub.5 includes
the acyl group and the other of R.sub.4 and R.sub.5 includes the
hydrocarbyl substitued acyl group, and R.sub.4 and R.sub.5 together
with the N atom to which they are attached, combine to form a ring
moiety. In other approaches, R.sub.4 and R.sub.5 together with the
N atom to which they are attached, combine to form a hydrocarbyl
substituted succinimide. M.sup.- is a carboxylate.
[0016] In yet another aspect of this disclosure, a method of
operating a fuel injected engine to provide improved engine
performance is described. The method includes combusting in the
engine a fuel composition including a major amount of fuel and
about 1 to about 100 ppm of a quaternary ammonium salt formed by
the reaction of an alkyl carboxylate with an amide or imide
compound obtained by reacting a hydrocarbyl substituted acylating
agent and an amine, wherein the amine has the structure of Formula
I or the resulting quaternary ammonium salt has the structure of
Formula II. In yet further aspects, a use of the quaternary
ammonium salts as described in the previous paragraphs is provided
to provide improved engine performance such as a reduced average
flow loss of about 45% or less as evaluated by XUD-9, a power
recovery of about 65 percent or greater as measured by a CEC
F-98-08 test modified to evaluate the ability of an additive to
restore power lost due to deposit formation, and/or removal of
carboxylate deposits and unsticking injectors on a cold start.
[0017] As used herein, the term "hydrocarbyl group" or
"hydrocarbyl" 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 a molecule and
having a predominantly hydrocarbon character. Examples of
hydrocarbyl groups include: (1) hydrocarbon substituents, that is,
aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
cycloalkenyl) substituents, and aromatic-, aliphatic-, and
alicyclic-substituted aromatic substituents, as well as cyclic
substituents wherein the ring is completed through another portion
of the molecule (e.g., two substituents together form an alicyclic
radical); (2) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of the description herein, do not alter the predominantly
hydrocarbon substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino,
alkylamino, and sulfoxy); (3) hetero-substituents, that is,
substituents which, while having a predominantly hydrocarbon
character, in the context of this description, contain other than
carbon in a ring or chain otherwise composed of carbon atoms.
Hetero-atoms include sulfur, oxygen, nitrogen, and encompass
substituents such as pyridyl, furyl, thienyl, and imidazolyl. In
general, no more than two, or as a further example, no more than
one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; in some embodiments, there
will be no non-hydrocarbon substituent in the hydrocarbyl
group.
[0018] 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.
Amine Compound
[0019] In one embodiment, the fuel additives herein are obtained
from a select amine having the structure of Formula I
##STR00007##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, and --C(O)NR'. R.sub.1 and R.sub.2
are independently alkyl groups containing 1 to 8 carbon atoms, and
R' is independently a hydrogen or a group selected from C.sub.1-6
aliphatic, phenyl, or alkylphenyl. In one approach, the select
amines of Formula 1 are at least diamines or triamines having a
terminal primary amino group on one end for reaction with the
hydrocarbyl substituted acylating agent and a terminal tertiary
amine on the other end for reaction with the quaternizing agent. In
other approaches, A includes 2 to 6 carbon units with one carbon
unit thereof replaced with a --O-- or a --NH-- group. Suitable
exemplary tertiary amine for forming the fuel additives herein may
be selected from 3-(2-(dimethylamino)ethoxy)propylamine,
N,N-dimethyl dipropylene triamine, and mixtures thereof. In other
embodiments or approaches, A has the structure
--(CH.sub.2).sub.r--[X--(CH.sub.2).sub.r'].sub.p-- with each of r,
r', and p independently being an integer 1, 2, 3, or 4 and X being
either oxygen or NR'' with R'' being hydrogen or a hydrocarbyl
group. In other embodiments, X is oxygen. In yet other embodiments,
X is --NH--.
[0020] The hydrocarbyl linker A preferably has 1 to 4 carbon units
replaced with the bivalent moiety described above, which is
preferably a --O-- or a --NH-- group. In other approaches, 1 to 2
carbon units of the hydrocarbyl linker A and, in yet further
approaches, 1 carbon unit of the hydrocarbyl linker A is replaced
with the bivalent moiety described herein. As appreciated, the
remainder of the hydrocarbyl linker A is preferably a carbon
atom(s). The number of carbon atoms on either side of the replaced
bivalent moiety need not be equal meaning the hydrocarbyl chain
between the terminal primary amino group and the terminal tertiary
amino group need not be symmetrical relative to the replaced
bivalent moiety.
Hydrocarbyl Substituted Acylating Agent
[0021] Any of the foregoing described tertiary amines may be
reacted with a hydrocarbyl substituted acylating agent that may be
selected from a hydrocarbyl substituted mono- di- or polycarboxylic
acid or a reactive equivalent thereof to form an amide or imide
compound. A particularly suitable acylating agent is a hydrocarbyl
substituted succinic acid, ester, anhydride, mono-acid/mono-ester,
or diacid. In some approaches, the hydrocarbyl substituted
acylating agent is a hydrocarbyl substituted dicarboxylic acid or
anhydride derivative thereof, a fatty acid, or mixtures
thereof.
[0022] In other approaches, the hydrocarbyl substituted acylating
agent may be carboxylic acid or anhydride reactant. In one
approach, the hydrocarbyl substituted acylating agent may be
selected from stearic acid, oleic acid, linoleic acid, linolenic
acid, palmitic acid, palmitoleic acid, lauric acid, myristic acid,
myristoleic acid, capric acid, caprylic acid, arachidic acid,
behenic acid, erucic acid, anhydride derivatives thereof, or a
combination thereof.
[0023] In one approach, the hydrocarbyl substituted acylating agent
is a hydrocarbyl substituted dicarboxylic anhydride of Formula
Iii
##STR00008##
wherein R.sub.6 is a hydrocarbyl or alkenyl group. In some aspects,
R.sub.6 is a hydrocarbyl group having a number average molecular
weight from about 200 to about 2500 For example, the number average
molecular weight of R.sub.6 may range from about 600 to about 1300,
as measured by GPC using polystyrene as a calibration reference. A
particularly useful R.sub.6 has a number average molecular weight
of about 1000 Daltons and comprises polyisobutylene.
[0024] The number average 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
was 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.
[0025] In some approaches, the R.sub.6 hydrocarbyl moiety may
comprise 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
formed from ethylene radicals, propylene radicals, butylene
radicals, pentene radicals, hexene radicals, octene radicals and
decene radicals. In some aspects, the R.sub.6 polyalkenyl radical
may be in the form of, for example, a homopolymer, copolymer or
terpolymer. In other aspects, the polyalkenyl radical is
polyisobutylene. For example, the polyalkenyl radical may be a
homopolymer of polyisobutylene comprising from about 5 to about 60
isobutylene groups, such as from about 15 to about 30 isobutylene
groups. The polyalkenyl compounds used to form the R.sub.6
polyalkenyl radicals may be formed by any suitable methods, such as
by conventional catalytic oligomerization of alkenes.
[0026] In some aspects, high reactivity polyisobutylenes having
relatively high proportions of polymer molecules with a terminal
vinylidene group may be used to form the R.sub.6 group. In one
example, at least about 60%, such as about 70% to about 90%, of the
polyisobutenes comprise terminal olefinic double bonds. 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 1.5 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 1.3.
Quaternizing Agent
[0027] A suitable alkylating or quaternizing agent is a
hydrocarbyl-substituted carboxylate, such as an alkyl carboxylate.
In some approaches or embodiments, the quaternizing agent is an
alkyl carboxylate selected form alkyl oxalate, alkyl salicylate,
and combinations thereof. In other approaches or embodiments, the
alkyl group of the alkyl carboxylate includes 1 to 6 carbon atoms,
and is preferably methyl groups.
[0028] For alkylation with an alkyl carboxylate, it may be
desirable in some approaches that the corresponding acid of the
carboxylate have a pKa of less than 4.2. For example, the
corresponding acid of the carboxylate may have a pKa of less than
3.8, such as less than 3.5, with a pKa of less than 3.1 being
particularly desirable. Examples of suitable carboxylates may
include, but not limited to, maleate, citrate, fumarate, phthalate,
1,2,4-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate,
nitrobenzoate, nicotinate, oxalate, aminoacetate, and salicylate.
As noted above, preferred carboxylates include oxalate, salicylate,
and combinations thereof.
Quaternary Ammonium Salt
[0029] In other approaches or embodiments, the quaternary ammonium
salt formed by the reaction of an alkyl carboxylate with an amide
or imide compound obtained by reacting a hydrocarbyl substitued
acylating agent and an amine of Formula 1 results in a quaternary
ammonium salt having the structure of Formula IV
##STR00009##
Wherein A is a hydrocarbyl linker with 2 to 10 carbon units and
including one or more carbon units thereof independently replaced
with a bivalent moiety selected from the group consisting of --O--,
--N(R')--, --C(O)--, --C(O)O--, or --C(O)NR'. R.sub.1, R.sub.2, and
R.sub.3 are independently alkyl groups containing 1 to 8 carbon
atoms; and R' is independently a hydrogen or a group selected from
C.sub.1-6 aliphatic, phenyl, or alkylphenyl. R.sub.4 and R.sub.5
are independently a hydrogen, an acyl group (RC(O)--), or a
hydrocarbyl substituted acyl group (the hydrocarbyl substituted
acyl group may be derived from a dicarboxylic acid as shown in the
exemplary formulas below). In some approaches or embodiments, if
one of R.sub.4 or R.sub.5 is hydrogen, then the other of R.sub.4
and R.sub.5 is the acyl group or the hydrocarbyl substituted acyl
group. In other approaches or embodiments, if both R.sub.4 and
R.sub.5 include carbonyl moieties, then one of R.sub.4 and R.sub.5
includes the acyl group and the other of R.sub.4 and R.sub.5
includes the hydrocarbyl substitued acyl group, and R.sub.4 and
R.sub.5 together with the N atom to which they are attached,
combine to form a ring moiety. The hydrocarbyl substituted acyl
group may include a terminal carboxyl group. M.sup.- is a
carboxylate, such as oxalate, salicylate, or combinations
thereof.
[0030] Suitable examples of the resulting quaternary ammonium salt
from the above described reactions include, but are not limited to
compounds of the following exemplary structures:
##STR00010##
Wherein A, R.sub.1, R.sub.2, R.sub.3, R.sub.6, and M are as
described above. R.sub.7 is a C1 to C30 hydrocarbyl group, and
R.sub.8 is a C1 to C10 hydrocarbyl linker. Due to the length of the
hydrocarbyl chain A and the presence of the replacing bivalent
moiety therein as discussed above, it is believed the quaternary
ammonium salts as described herein include a relatively sterically
available quaternary nitrogen that is more available for detergent
activity than prior quaternary ammonium compounds.
[0031] When formulating the fuel compositions of this application,
the above described additives (reaction products and/or resultant
additives as described above) 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. In some aspects, the fuels may contain minor
amounts of the above described reaction product or resulting salt
thereof that controls or reduces the formation of engine deposits,
for example injector deposits in engines. For example, any
embodiments of the fuels of this disclosure may contain, on an
active ingredient basis, an amount of the quaternary ammonium salt
(or reaction product as described herein) in the range of about 1
ppm to about 100 ppm, in other approaches, about 5 ppm to about 50
ppm, in yet further approaches about 10 ppm to about 25 ppm of the
quaternary ammonium salt. 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 active
ingredient basis 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.
Other Additives
[0032] 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 additives. Similarly, the fuels may
contain suitable amounts of conventional fuel blending components
such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and the
like.
[0033] 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, tort-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.
[0034] 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.
[0035] 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. Nos. 5,575,823 and
3,015,668 both of which disclosures are herein incorporated by
reference in their entirety.
[0036] 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, 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.
[0037] The additives of the present application, including the
quaternary ammonium salts described above, and optional additives
used in formulating the fuels of this invention may be blended into
the base fuel individually or in various sub-combinations. 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
[0038] The fuels of the present application may be applicable to
the operation of diesel, jet, or gasoline engines. In one approach,
the quaternary ammonium salts herein are well suited for diesel or
gasoline as shown in the Examples. In one embodiment, the fuel is
diesel fuel. In another embodiment, the fuel is gasoline. In yet
another embodiment, the fuel is a jet fuel. 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. "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.
[0039] The fuels herein are suitable for use in various internal
combustion systems or engines. The systems or 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.). By combustion
system or engine herein is meant, internal combustion engines, for
example and not by limitation, Atkinson cycle engines, rotary
engines, spray guided, wall guided, and the combined wall/spray
guided direct injection gasoline ("DIG" or "GDI") engines,
turbocharged DIG engines, supercharged DIG engines, homogeneous
combustion DIG engines, homogeneous/stratified DIG engines, DIG
engines outfitted with piezoinjectors with capability of multiple
fuel pulses per injection, DIG engines with EGR, DIG engines with a
lean-NOx trap, DIG engines with a lean-NOx catalyst, DIG engines
with SN--CR. NOx control, DIG engines with exhaust diesel fuel
after-injection (post combustion) for NOx control, DIG engines
outfitted for flex fuel operation (for example, gasoline, ethanol,
methanol, biofuels, synthetic fuels, natural gas, liquefied
petroleum gas (LPG), and mixtures thereof.) Also included are
conventional and advanced port-fueled internal combustion engines,
with and without advanced exhaust after-treatment systems
capability, with and without turbochargers, with and without
superchargers, with and without combined supercharges turbocharger,
with and without on-board capability to deliver additive for
combustion and emissions improvements, and with and without
variable valve timing. Further included are gasoline fueled
homogeneous charge compression ignition (HCCI) engines, diesel HCCI
engines, two-stroke engines, diesel fuel engines, gasoline fuel
engines, stationary generators, gasoline and diesel HCCI,
supercharged, turbocharged, gasoline and diesel direct injection
engines, engines capably of variable valve timing, leanburn
engines, engines capable of inactivating cylinders or any other
internal combustion engine. Still further examples of combustion
systems include any of the above-listed systems combined in a
hybrid vehicle with an electric motor.
[0040] Accordingly, aspects of the present application are directed
to methods of or the use of the quaternary ammonium compounds
herein for reducing injector deposits in an internal combustion
system or engine or within a fuel system for an internal combustion
system or engine, cleaning-up fouled injectors, or un-sticking
injectors. In another aspect, the quaternary ammonium compounds
described herein or fuel containing the quaternary ammonium
compounds herein may be combined with one or more of
polyhydrocarbyl-succinimides, -acids, -amides, -esters,
-amide/acids and -acid/esters, reaction products of polyhydrocarbyl
succinic anhydride and aminoguanidine and its salts, Mannich
compounds, and mixtures thereof. In other aspects, the methods or
use include injecting a hydrocarbon-based fuel comprising a
quaternary ammonium compounds of the present disclosure through the
injectors of the engine into the combustion chamber, and igniting
the fuel to prevent or remove deposits on fuel injectors, to
clean-up fouled injectors, and/or to unstick injectors. In some
aspects, the method may also comprise mixing into the fuel at least
one of the optional additional ingredients described above.
EXAMPLES
[0041] 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.
Comparative Example 1
[0042] A comparative quaternary ammonium salt was prepared in a
manner consistent to various examples (e.g., Example 2, Example 10,
etc.) in EP 2 531 580 B1. Comparative preparative additive A (a
comparative preparatory polyisobutenyl succinimide, PIBSI) was
prepared as follows: 207.95 grams (0.218 equivalents of anhydride)
of polyisobutenyl succinic anhydride (PIMA, made with about 1000
average MW polyisobutylene, PIB, and maleic anhydride) and 92.60
grams of toluene were charged in a 1 liter reaction flask equipped
with Dean-Stark trap. Under nitrogen, the mixture was stirred and
heated to 90.degree. C. Over about 10 minutes, 22.30 grams of
dimethylamino propylamine (DMAPA) was added. The temperature was
increased to about 165.degree. C. and held for 4 hours while
removing water. Toluene was removed under vacuum. IR spectroscopy
of the product confirmed formation of the succinimide.
[0043] Comparative additive B (a comparative quaternary ammonium
salt) was prepared as follows: 100.53 grams (0.0970 moles) of
Additive A and 14.76 grams (0.0970 moles) of methyl salicylate were
charged in a 250 ml reaction flask. The mixture was heated under
nitrogen to 140.degree. C. and held for 7 hours. .sup.1H NMR
spectroscopy of the product confirmed formation of a quaternary
ammonium salt.
Example 1
[0044] Additive C (preparatory oleyl amide) was prepared as
follows: 249.05 grams (0.882 moles) of oleic acid and 60.35 grams
of toluene where charged in a 1 liter reaction flask equipped with
Dean-Stark trap. Under nitrogen, the mixture was stirred and heated
to 100.degree. C. Over about 20 minutes, 128.77 grams (0.882 moles)
of 3-(2-(dimethylamino)ethoxy) propylamine (DMAEPA) was added. The
temperature was increased to about 165.degree. C. and held for 4
hours while removing water. Toluene was removed under vacuum. IR
spectroscopy of the product confirmed formation of the amide.
[0045] Additive D (an inventive quaternary ammonium salt) was
prepared as follows: 7.50 grams (0.0183 moles) of Additive C and
2.80 grams (0.0184 moles) of methyl salicylate were charged in a
thick walled glass tube and sealed. The mixture was heated under
nitrogen to 140.degree. C. and held for 12 hours. .sup.1H NMR
spectroscopy of the product confirmed formation of the quaternary
ammonium salt.
Example 2
[0046] Additive E (preparatory ASA succinimide) was prepared as
follows: 270.93 grams (0.679 equivalents of anhydride) of a
C.sub.20-24 alkenyl succinic anhydride (ASA) and 105.73 grams of
toluene were charged in a 1 liter reaction flask equipped with
Dean-Stark trap. Under nitrogen, the mixture was stirred and heated
to 100.degree. C. Over about 15 minutes, 99.13 grams (0.679 moles)
of 3-(2-(dimethylamino)ethoxy)propylamine (DMAEPA) was added. The
temperature was increased to about 160.degree. C. and held for 4
hours while removing water. Toluene was removed under vacuum. IR
spectroscopy of the product confirmed formation of the amide.
[0047] Additive F (inventive quaternary ammonium salt) was prepared
as follows: 106.71 grams (0.202 moles) of Additive E and 30.78
grams (0.202 moles) of methyl salicylate were charged in a 250 ml
reaction flask. The mixture was heated under nitrogen to
140.degree. C. and held for 6 hours. .sup.1H NMR spectroscopy of
the product confirmed formation of the quaternary ammonium
salt.
Example 3
[0048] Additive G (preparatory PIBSI) was prepared as follows:
207.75 grams (0.218 equivalents of anhydride) of PIBSA (made with
about 1000 MW PIB and maleic anhydride) and 67.96 grams of toluene
were charged in a 1 liter reaction flask equipped with Dean-Stark
trap. Under nitrogen, the mixture was stirred and heated to
100.degree. C. Over about 15 minutes, 30.24 grams (0.207 moles) of
3-(2-(dimethylamino)ethoxy)propylamine (DMAEPA) was added. The
temperature was increased to about 160.degree. C. and held for 3
hours while removing water. Toluene was removed under vacuum. IR
spectroscopy of the product confirmed formation of the
succinimide.
[0049] Additive H (inventive quaternary ammonium salt) was prepared
as follows: 67.20 grams (0.057 moles) of Additive G and 8.69 grams
(0.057 moles) of methyl salicylate were charged in a 250 ml
reaction flask. The mixture was heated under nitrogen to
140.degree. C. and held for 6 hours. .sup.1H NMR spectroscopy of
the product confirmed formation of the quaternary ammonium
salt.
Example 4
[0050] Additive I (preparatory PIBSI) was prepared as follows:
287.50 grams (0.126 equivalents of anhydride) of PIBSA (made with
2300 MW PIB and maleic anhydride) and 96.15 grams of toluene were
charged in a 1 liter reaction flask equipped with Dean-Stark trap.
Under nitrogen, the mixture was stirred and heated to 100.degree.
C. Over about 5 minutes, 18.20 grams (0.125 moles) of
3-(2-(dimethylamino)ethoxy)propylamine (DMAEPA) was added. The
temperature was increased to about 160.degree. C. and held for 4
hours while removing water. Toluene was removed under vacuum. IR
spectroscopy of the product confirmed formation of the
succinimide.
[0051] Additive J (inventive quaternary ammonium salt) was prepared
as follows: 95.37 grams (0.0396 moles) of Additive I and 6.02 grams
(0.0396 moles) of methyl salicylate were charged in a 250 ml
reaction flask. The mixture was heated under nitrogen to
140.degree. C. and held for 6 hours. .sup.1H NMR spectroscopy of
the product confirmed formation of the quaternary ammonium
salt.
Example 5
[0052] Additive K (preparatory PIBSI) was prepared as follows:
283.62 grams (0.298 equivalents of anhydride) of PIBSA (made with
about 1000 MW PIB and maleic anhydride) and 82.31 grams of toluene
were charged in a 1 liter reaction flask equipped with Dean-Stark
trap. Under nitrogen, the mixture was stirred and heated to
100.degree. C. Over about 15 minutes, 47.37 grams (0.298 moles) of
N,N dimethyldipropylene triamine (DMAPAPA) was added. The
temperature was increased to about 160.degree. C. and held for 2
hours while removing water. Toluene was removed under vacuum. IR
spectroscopy of the product confirmed formation of the
succinimide.
[0053] Additive L (inventive quaternary ammonium salt) was prepared
as follows: 78.31 grams (0.0717 moles) of Additive K and 10.90
grams (0.0717 moles) of methyl salicylate were charged into a 250
ml reaction flask. The mixture was heated under nitrogen to
160.degree. C. and held for 6 hours. .sup.1H NMR spectroscopy of
the product confirmed formation of the quaternary ammonium
salt.
Example 6
[0054] The above quaternary ammonium salt additives from the
comparative and inventive Examples were evaluated in a diesel fuel
using an XUD-9 test (CEC F-23-A-01). The XUD-9 test method
evaluates the capability of a fuel to control the formation of
deposits on the injector nozzles of an indirect injection diesel
engine. Results of tests run according to the XUD-9 test method
were expressed in terms of the percentage airflow loss at various
injector needle lift points. Airflow measurements were accomplished
with an airflow rig complying with ISO 4010.
[0055] Prior to conducting the test, the injector nozzles were
cleaned and checked for airflow at 0.05, 0.1, 0.2, 0.3 and 0.4 mm
lift. Nozzles were discarded if the airflow was outside of the
range 250 ml/min to 320 ml/min at 0.1 mm lift. The nozzles were
assembled into the injector bodies and the opening pressures set to
115.+-.5 bar. A slave set of injectors was also fitted to the
engine. The previous test fuel was drained form the system. The
engine was run for 25 minutes in order to flush through the fuel
system. During this time all the spill-off fuel was discarded and
not returned. The engine was then set to test speed and load and
all specified parameters checked and adjusted to the test
specification. The slave injectors were then replaced with the test
units. Air flow was measured before and after the test. An average
of 4 injector flows at 0.1 mm lift was used to calculate the
percent of fouling. The degree of flow remaining=100-percent of
fouling. The results are provided in Table 1 below.
TABLE-US-00001 TABLE 1 XUD-9 Test Results Active Treat Rate Average
Flow Loss Additive (ppm by wt) (%) None -- 70 B (Comparative) 15 45
D 10 9 F 10 36 H 10 10 H 15 5 H 30 0 J 15 43 L 15 45
[0056] All of the inventive additives performed as well as or
better (had the same or lower flow loss) than the comparative
additive. Moreover, certain inventive additives demonstrated
dramatically improved detergency at a lower treat rate that the
comparative additives.
Example 7
[0057] A DW-10B diesel engine was also run to determine the
inventive additives ability to clean up fouled injectors using a
test outlined in CEC F-98-08. Using the test cycle and dopant (1
ppm Zn as zinc neodecanoate) used in CEC F-98-08, inventive
additives H and D were evaluated for their ability in diesel fuel
to remove (clean up) deposits. To perform this evaluation, the
engine was first run with zinc dopant in the fuel, resulting in a
power loss due to fouling of the injector holes. Then, the engine
was run on fuel containing both the zinc dopant and detergent
additive(s). A more detailed description of this protocol can be
found in U.S. Pat. No. 8,894,726 B2 (Column 9), which is
incorporated herein by reference and further discussed below. The
results are shown in Table 3.
[0058] Diesel Engine Test Protocol:
[0059] The DW-10 test was developed by Coordinating European
Council (CEC) to demonstrate the propensity of fuels to provoke
fuel injector fouling and can also be used to demonstrate the
ability of certain fuel additives to prevent or control these
deposits. Additive evaluations used the protocol of CEC F-98-08 for
direct injection, common rail diesel engine nozzle coking tests. An
engine dynamometer test stand was used for the installation of the
Peugeot DW10 diesel engine for running the injector coking tests.
The engine was a 2.0 liter engine having four cylinders. Each
combustion chamber had four valves and the fuel injectors were DI
piezo injectors that have a Euro V classification.
[0060] The core protocol procedure consisted of running the engine
through a cycle for 8-hours and allowing the engine to soak (engine
off) for a prescribed amount of time. The foregoing sequence was
repeated four times. At the end of each hour, a power measurement
was taken of the engine while the engine was operating at rated
conditions. The injector fouling propensity of the fuel was
characterized by a difference in observed rated power between the
beginning and the end of the test cycle.
[0061] Test preparation involved flushing the previous test's fuel
from the engine prior to removing the injectors. The test injectors
were inspected, cleaned, and reinstalled in the engine. If new
injectors were selected, the new injectors were put through a
16-hour break-in cycle. Next, the engine was started using the
desired test cycle program. Once the engine was warmed up, power
was measured at 4,000 RPM and full load to check for full power
restoration after cleaning the injectors. If the power measurements
were within specification, the test cycle was initiated. Table 2
below provides a representation of the DW-10 coking cycle that was
used to evaluate the fuel additives according to the
disclosure.
TABLE-US-00002 TABLE 2 One hour representation of DW-10 coking
cycle Duration Engine Boost air after Step (minutes) speed (rpm)
Load (%) Torque (Nm) Intercooler (.degree. C.) 1 2 1750 20 62 45 2
7 3000 60 173 50 3 2 1750 20 62 45 4 7 3500 80 212 50 5 2 1750 20
62 45 6 10 4000 100 * 50 7 2 1250 10 25 43 8 7 3000 100 * 50 9 2
1250 10 25 43 10 10 2000 100 * 50 11 2 1250 10 25 43 12 7 4000 100
* 50
[0062] Fuel additives D and H from Examples 1 and 3 were tested
using the foregoing engine test procedure in an ultra-low sulfur
diesel fuel containing zinc neodecanoate, 2-ethylhexyl nitrate, and
a fatty acid ester friction modifier (base fuel). A "dirty-up"
phase consisting of base fuel only with no additive was initiated,
followed by a "clean-up" phase consisting of base fuel plus
additive as noted in Table 3 below. All runs were made with 8 hour
dirty-up and 8 hour clean-up unless indicated otherwise. The
percent power recovery was calculated using the power measurement
at end of the "dirty-up" phase and the power measurement at end of
the "clean-up" phase. The percent power recovery was determined by
the following formula: Percent Power recovery=(DU-CU)/DU.times.100,
wherein DU is a percent power loss at the end of a dirty-up phase
without the additive, CU is the percent power at the end of a
clean-up phase with the fuel additive, and power is measured
according to CEC F98-08 DW10 test.
TABLE-US-00003 TABLE 3 DW-10B Test Results - Clean Up Power Loss
Active Treat Power Loss after 8 hours Power Rate(s) after Dirty Up
of Clean Up Recovery Additive(s) (ppm by wt) (%) (%) (%) H 45 4.53
0.59 87 H and D 30 and 5 5.80 2.03 65
Example 8
[0063] Another evaluation involving the DW-10B test was run to
determine the additives ability to remove carboxylate deposits in a
diesel engine. These types of deposits can form on internal moving
parts causing injector sticking on cold start. A description of the
test protocol can be found in U.S. Pat. No. 8,529,643 B2 (Columns
11-12), which is incorporated herein by reference and further
discussed below, with the exception that the fouling dopants were
0.5 ppm by wt sodium as sodium naphthenate and 10 ppm by wt
dodecenyl succinic acid (DDSA).
[0064] In this example, the effect of inventive additives on diesel
fuel contaminated with carboxylate salts for high pressure common
rail diesel fuel systems was evaluated. An engine test was used to
demonstrate the propensity of fuels to provoke fuel injector
sticking and was also used to demonstrate the ability of certain
fuel additives to prevent or control the internal deposits in the
injectors. An engine dynamometer test stand was used for the
installation of a Peugeot DW10 diesel engine for running the
injector sticking tests. The engine was a 2.0 liter engine having
four cylinders. Each combustion chamber had four valves and the
fuel injectors were DI piezo injectors have a Euro V
classification.
[0065] The core protocol procedure consisted of running the engine
through a cycle for 8-hours and allowing the engine to soak (engine
off) for a prescribed amount of time. The injector performance was
then characterized by measuring the cylinder exhaust temperature
for each cylinder. A test was stopped and considered to have failed
(one or more injectors sticking) if the exhaust temperature of any
cylinder was more than 65.degree. C. above any other cylinder
exhaust temperature at any point in time. A test was also
considered to have failed if after allowing the engine to cool to
ambient temperature, a cold start showed a temperature difference
of 45.degree. C. or more in cylinder exhaust temperatures. Sticking
of the needle and thus failure could also be confirmed by
disassembling the injector and subjectively determining the force
required to remove the needle from the nozzle housing. Cleanliness
tests were run for keep-clean performance as well as clean-up
performance.
[0066] Test preparation involved flushing the previous test's fuel
from the engine prior to removing the injectors. The test injectors
were inspected, cleaned, and reinstalled in the engine. If new
injectors were selected, the new injectors were put through a
16-hour break-in cycle. Next, the engine was started using the
desired test cycle program. Once the engine was warmed up, power
was measured at 4,000 RPM and full load to check for full power
restoration after cleaning the injectors. If the power measurements
were within specification, the test cycle was initiated.
[0067] The diesel engine nozzle sticking tests were conducted using
the Peugeot DW-10 engine following the protocol of Table 2 above.
For keep-clean testing, the engine was run with diesel fuel
contaminated with metal carboxylate salts and with the detergent
additive indicated in Table 5 below. For clean-up testing, the
engine was first run with diesel fuel contaminated with metal
carboxylate salts without a detergent additive to establish a
baseline of stuck fuel injectors. Next, the engine was run with the
same fuel containing the detergent additive indicated. In all of
the tests, the fuels tested contained 200 ppmv lubricity modifier
and 1600 ppmv cetane improver, 0.5 ppmw sodium as sodium
naphthenate and 10 ppmw dodecenyl succinic acid (DDSA), 3 ppmw of
NaOH, and 25 ppmwv of water. At the beginning of the test, no
injector sticking was indicated by a uniform exhaust gas
temperature for all 4-cylinders as shown in Table 5 below. However,
a cold start of the engine after 8 hours showed injector sticking
as also shown in Table 5 due to the increased temperature
differential between the cylinders. As also shown in Table 5,
Detergent Additive H greatly reduced the maximum exhaust gas
temperature difference, indicating that the injectors were no
longer sticking.
TABLE-US-00004 TABLE 5 DW-10B Test Results - Carboxylate Deposit
Removal Active Maximum Exhaust Detergent Gas Temperature Engine Run
Additive Difference on Time Detergent Treat Rate Cold Start (hrs)
Dopants Additive (ppm by wt) (.degree. C.) Start of Test None None
-- 11 16 Na/DDSA None -- 78 24 Na/DDSA H 45 25 32 Na/DDSA H 45
22
Example 9
[0068] Inventive additive H from Example 3 above was further tested
for its ability to clean-up fouled injectors in a gasoline direct
injection (GDI) 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 and discussed further below.
[0069] The GDI testing involved the use of a fuel blend to
accelerate the dirty-up phase or injector fouling of the GDI
engine. The accelerated fuel 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 2.4 L,
16 valve, inline 4 gasoline 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 6 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 GDI testing are shown below in
Table 7.
TABLE-US-00005 TABLE 6 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)
TABLE-US-00006 TABLE 7 GDI Test Results Change in LTFT Vehicle
Miles from Start of Detergent Additive Treat Accumulated test with
clean Clean Test # Segment Phase Additive Rate, ppmw During Segment
injectors (%) Up (%) 1 1 Dirty Up None (Base) -- 4453 9.13 2 Clean
Up Additive H 30 1029 0.93 90 2 1 Dirty Up None (Base) -- 3641 7.93
2 Clean Up Additive H 15 1029 3.75 53
[0070] 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
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] 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.
[0076] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or can be presently unforeseen can
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they can be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *