U.S. patent application number 17/368918 was filed with the patent office on 2022-05-12 for fuel additives for mitigating injector nozzle fouling and reducing particulate emissions.
This patent application is currently assigned to CHEVRON ORONITE COMPANY LLC. The applicant listed for this patent is CHEVRON ORONITE COMPANY LLC, CHEVRON U.S.A. INC.. Invention is credited to Carrie Y. CHAN, Peter A. FUENTES-AFFLICK, Theresa Liang GUNAWAN, Andrew M. ICKES, Chung-Hao KUO, Man Kit NG, William Raymond RUHE, JR..
Application Number | 20220145199 17/368918 |
Document ID | / |
Family ID | 1000006123495 |
Filed Date | 2022-05-12 |
United States Patent
Application |
20220145199 |
Kind Code |
A1 |
KUO; Chung-Hao ; et
al. |
May 12, 2022 |
FUEL ADDITIVES FOR MITIGATING INJECTOR NOZZLE FOULING AND REDUCING
PARTICULATE EMISSIONS
Abstract
The present disclosure provides a fuel composition that includes
hydrocarbon-based fuel boiling in the gasoline or diesel range; an
amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein the additive is
present in about 10 ppm to about 750 ppm by weight based on total
weight of the fuel composition; wherein R.sub.1 is a
hydrocarbylgroup having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and one or more
nitrogen-containing detergent.
Inventors: |
KUO; Chung-Hao; (Albany,
CA) ; RUHE, JR.; William Raymond; (Benica, CA)
; NG; Man Kit; (El Sobrante, CA) ;
FUENTES-AFFLICK; Peter A.; (San Francisco, CA) ;
ICKES; Andrew M.; (Kensington, CA) ; CHAN; Carrie
Y.; (Daly City, CA) ; GUNAWAN; Theresa Liang;
(Berkeley, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CHEVRON ORONITE COMPANY LLC
CHEVRON U.S.A. INC. |
San Ramon
San Ramon |
CA
CA |
US
US |
|
|
Assignee: |
CHEVRON ORONITE COMPANY LLC
San Ramon
CA
CHEVRON U.S.A. INC
San Ramon
CA
|
Family ID: |
1000006123495 |
Appl. No.: |
17/368918 |
Filed: |
July 7, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63048922 |
Jul 7, 2020 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 10/04 20130101;
C10L 1/2225 20130101; C10L 1/2222 20130101; C10L 10/02
20130101 |
International
Class: |
C10L 1/222 20060101
C10L001/222; C10L 10/04 20060101 C10L010/04; C10L 10/02 20060101
C10L010/02 |
Claims
1. A fuel composition comprising: a hydrocarbon-based fuel boiling
in the gasoline or diesel range; an amine-based detergent given by
formula R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein the
amine-based detergent is present in about 10 ppm to about 750 ppm
by weight based on total weight of the fuel composition; wherein
R.sub.1 is a hydrocarbyl group having 8 to 20 carbons, R.sub.2 is
hydrogen or (CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are
independently integers having a value of 3 or greater; and one or
more nitrogen-containing detergent.
2. The fuel composition of claim 1, wherein R.sub.1 is linear or
branched.
3. The fuel composition of claim 1, wherein the one or more
nitrogen-containing detergent is an aliphatic hydrocarbyl amine,
hydrocarbyl-substituted poly(oxyalkylene)amine,
hydrocarbyl-substituted succinimide, Mannich reaction product,
nitro and amino aromatic ester of polyalkylphenoxyalkanol, or
polyalkylphenoxyaminoalkane.
3. The fuel composition of claim 1, wherein the amine-based
detergent or the one or more nitrogen-containing detergent is a
monoamine or a polyamine.
4. The fuel composition of claim 1, wherein the amine-based
detergent is present in about 10 ppm to 750 ppm of the fuel
composition.
5. The fuel composition of claim 1, wherein the one or more
nitrogen-containing detergent is present in about 50 ppm to about
2500 ppm of the fuel composition.
6. The fuel composition of claim 1, further comprising
antioxidants, metal deactivators, demulsifiers, oxygenates,
antiknock agents, dispersants, pour point depressants, or flow
improvers.
7. A concentrate composition comprising: about 30 to 90 wt % of an
organic solvent boiling in a range of from 65.degree. C. to
205.degree. C. and; about 10 to 70 wt % of a detergent mixture
comprising: (1) an amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein R.sub.1 is a
hydrocarbyl group having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and (2) one or more
nitrogen-containing detergent.
8. The concentrate composition of claim 7, wherein R.sub.1 is
linear or branched.
9. The concentrate composition of claim 7, wherein the one or more
nitrogen-containing detergent is an aliphatic hydrocarbyl amine,
hydrocarbyl-substituted poly(oxyalkylene)amine,
hydrocarbyl-substituted succinimide, Mannich reaction product,
nitro and amino aromatic ester of polyalkylphenoxyalkanol, or
polyalkylphenoxyaminoalkane.
10. The concentrate composition of claim 7, wherein the amine-based
detergent or the one or more nitrogen-containing detergent is a
monoamine or a polyamine.
11. A method of controlling injector fouling, the method
comprising: supplying to a direct injection engine a fuel
composition comprising: a hydrocarbon-based fuel boiling in the
gasoline or diesel range; an amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein the amine-based
detergent is present in about 10 ppm to about 750 ppm by weight
based on total weight of the fuel composition; wherein R.sub.1 is a
hydrocarbyl group having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and one or more
nitrogen-containing detergent.
12. The method of claim 11, wherein R.sub.1 is linear or
branched.
13. The method of claim 11, wherein the one or more
nitrogen-containing detergent is an aliphatic hydrocarbyl amine,
hydrocarbyl-substituted poly(oxyalkylene)amine,
hydrocarbyl-substituted succinimide, Mannich reaction product,
nitro and amino aromatic ester of polyalkylphenoxyalkanol, or
polyalkylphenoxyaminoalkane.
13. The method of claim 11, wherein the amine-based detergent or
the one or more nitrogen-containing detergent is a monoamine or a
polyamine.
14. The method of claim 11, wherein the amine-based detergent is
present in about 10 ppm to 750 ppm of the fuel composition.
15. The method of claim 11, wherein the one or more
nitrogen-containing detergent is present in about 50 ppm to about
2500 ppm of the fuel composition.
16. The method of claim 11, wherein the fuel composition further
comprises antioxidants, metal deactivators, demulsifiers,
oxygenates, antiknock agents, dispersants, pour point depressants,
or flow improvers.
Description
TECHNICAL FIELD
[0001] This disclosure relates to fuel components that can improve
engine performance. More specifically, this disclosure describes
compositions and methods for mitigating injector nozzle fouling and
reducing particulate emissions in direct injection spark ignition
engines.
BACKGROUND
[0002] Traditional fuel additives developed for port fuel injection
(PFI) gasoline engines are generally not optimized for controlling
formation of deposits in direct injection spark ignition (DISI)
engines, sometimes referred to as direct injection gasoline (DIG)
or gasoline injection (GDI) engines. This is largely due to the
fact that unlike PFI engines, DISI engines deliver fuel directly
into the combustion chamber. When fuel is directly injected, it is
immediately exposed to high temperatures and pressures. In this
environment, combustion products can accumulate on the external
and/or internal surfaces of the injector and nozzle (known as
injector fouling).
[0003] The formation of deposits, both around the injector nozzle
and inside the combustion chamber, can have significant negative
impact on one or more of fuel flow rate, injection duration, and/or
spray pattern. This, in turn, can lead to increased emission,
increased particulate matter (PM) formation, reduced fuel economy,
loss of power/performance, increased wear, and/or reduced equipment
life.
SUMMARY
[0004] In one aspect, there is provided a fuel composition
comprising: a hydrocarbon-based fuel boiling in the gasoline or
diesel range; an amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein the detergent is
present in about 10 ppm to about 750 ppm by weight based on total
weight of the fuel composition; wherein R.sub.1 is a hydrocarbyl
group having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and one or more
nitrogen-containing detergent.
[0005] In another aspect, there is provided a concentrate
composition comprising: about 30 to 90 wt % of an organic solvent
boiling in a range of from 65.degree. C. to 205.degree. C. and;
about 10 to 70 wt % of a detergent mixture comprising: (1) an
amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein R.sub.1 is a
hydrocarbyl group having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and (2) one or more
nitrogen-containing detergent.
[0006] In yet another aspect, there is provided a method of
controlling injector fouling, the method comprising: supplying to a
direct injection engine a fuel composition comprising: a
hydrocarbon-based fuel boiling in the gasoline or diesel range; an
amine-based detergent given by formula
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2, wherein the amine-based
detergent is present in about 10 ppm to about 750 ppm by weight
based on total weight of the fuel composition; wherein R.sub.1 is a
hydrocarbyl group having 8 to 20 carbons, R.sub.2 is hydrogen or
(CH.sub.2).sub.nNH.sub.2 moiety, and wherein m, n are independently
integers having a value of 3 or greater; and one or more
nitrogen-containing detergent.
BRIEF DESCRIPTION OF DRAWINGS
[0007] FIG. 1 is an illustration described in the Example
section.
[0008] FIG. 2 is an illustration described in the Example
section.
[0009] FIG. 3 is an illustration described in the Example
section.
[0010] FIG. 4 is an illustration described in the Example
section.
[0011] FIGS. 5A-5C are illustrations described in the Example
section.
[0012] FIGS. 6A-6C are illustrations described in the Example
section.
[0013] FIGS. 7A-7C are illustrations described in the Example
section.
[0014] FIGS. 8A-8C are illustrations described in the Example
section.
[0015] FIGS. 9A-9C are illustrations described in the Example
section.
[0016] FIGS. 10A-10C are illustrations described in the Example
section.
[0017] FIGS. 11A-11B are illustrations described in the Example
section.
[0018] FIG. 12 is an illustration described in the Example
section.
DETAILED DESCRIPTION
[0019] The present invention describes compositions and methods for
deposit control in direct injection engines. More specifically, the
present invention provides detergent additive compositions that can
be utilized as components of fuel compositions and methods of using
the compositions thereof.
[0020] The fuel composition of the present invention comprises (i)
a hydrocarbon-based fuel, (ii) a primary fuel additive and (iii)
one or more secondary fuel additives.
[0021] Hydrocarbon-Based Fuel
[0022] The hydrocarbon-based fuel includes gasoline and diesel.
[0023] Gasoline fuel refers to a composition containing at least
predominantly C.sub.4-C.sub.12 hydrocarbons. In one embodiment,
gasoline or gasoline boiling range components is further defined to
refer to a composition containing at least predominantly
C.sub.4-C.sub.12 hydrocarbons and further having a boiling range of
from about 37.8.degree. C. (100.degree. F.) to about 204.degree. C.
(400.degree. F.). In an alternative embodiment, gasoline is defined
to refer to a composition containing at least predominantly
C.sub.4-C.sub.12 hydrocarbons, having a boiling range of from about
37.8.degree. C. (100.degree. F.) to about 204.degree. C.
(400.degree. F.), and further defined to meet ASTM D4814.
[0024] Diesel fuel refers to middle distillate fuels containing at
least predominantly C.sub.10-C.sub.25 hydrocarbons. In one
embodiment, diesel is further defined to refer to a composition
containing at least predominantly C.sub.10-C.sub.25 hydrocarbons,
and further having a boiling range of from about 165.6.degree. C.
(330.degree. F.) to about 371.1.degree. C. (700.degree. F.). In an
alternative embodiment, diesel is as defined above to refer to a
composition containing at least predominantly C.sub.10-C.sub.25
hydrocarbons, having a boiling range of from about 165.6.degree. C.
(330.degree. F.) to about 371.1.degree. C. (700.degree. F.), and
further defined to meet ASTM D975.
[0025] The hydrocarbon-based fuel is present in a major amount by
weight % of the total fuel composition. In some embodiments, the
hydrocarbon-based fuel is present in about 50 wt % or greater, 55
wt % or greater, 60 wt % or greater, 65 wt % or greater, 70 wt % or
greater, 75 wt % or greater, 80 wt % or greater, 85 wt % or
greater, 90 wt % or greater, 95 wt % or greater or between any
range from about 50 wt % to up to below 100 wt %.
[0026] According to some embodiments, the gasoline employed in the
present invention may be clean burning gasoline (CBG). CBG refers
to gasoline formulations that contain reduced levels of sulfur,
aromatics and olefins. The exact formulation may vary depending on
local regulatory definitions.
[0027] A fuel-soluble, non-volatile carrier fluid or oil may also
be used with compounds of this disclosure. The carrier fluid is a
chemically inert hydrocarbon-soluble liquid vehicle which
substantially increases the non-volatile residue (NVR), or
solvent-free liquid fraction of the fuel additive composition while
not overwhelmingly contributing to octane requirement increase. The
carrier fluid may be a natural or synthetic oil, such as mineral
oil, refined petroleum oils, synthetic polyalkanes and alkenes,
including hydrogenated and unhydrogenated polyalphaolefins,
synthetic polyoxyalkylene-derived oils, such as those described in
U.S. Pat. Nos. 3,756,793; 4,191,537; and 5,004,478; and in European
Patent Appl. Pub. Nos. 356,726 and 382,159.
[0028] The carrier fluids may be employed in amounts ranging from
35 to 5000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000
ppm of the fuel). When employed in a fuel concentrate, carrier
fluids may be present in amounts ranging from 20 to 60 wt % (e.g.,
30 to 50 wt %).
[0029] Primary Fuel Additive
[0030] The primary fuel additive of the present invention is an
amine-based detergent (more specifically, a linear/branched
aliphatic ether amine) having the following formula:
R.sub.1--O--(CH.sub.2).sub.m--NHR.sub.2 Formula I
where R.sub.1 is a hydrocarbyl group having 8 to 20 carbons,
R.sub.2 is hydrogen or (CH.sub.2).sub.nNH.sub.2 moiety, and m, n
are independently integers having a value of 3 or greater. The
hydrocarbyl group may be saturated or unsaturated. In some
embodiments, the hydrocarbyl group may contain more than one
unsaturated bond.
[0031] As an advantage, the fuel additives of the present invention
can deliver more basic nitrogen at the same treat rate compared to
conventional amine-based fuel detergents (such as
polyisobutylamine, polyether amine, etc.). This feature is
important in determining detergency. As another advantage, the low
molecular weight of the additives of the present invention along
with their low decomposition temperature and high volatility
prevents the additives from generating harmful deposits.
[0032] Particularly illustrative aliphatic ether amines compatible
with the present invention include isotridecyloxypropylamine and
2-ethylhexyloxypropyl amine. These are illustrative examples that
are not intended to be limiting.
[0033] In some embodiments, the primary fuel additive can be
present in about 10 ppm to about 750 ppm (such as 20 to 700, 30 to
650, 50 to 600, 100 to 500, 200 to 400, 250 to 350, and so forth)
based on the total fuel composition.
[0034] Secondary Fuel Additive
[0035] The fuel composition of the present invention includes one
or more secondary fuel additives. The secondary fuel additive is a
nitrogen-containing detergent that provides enhanced detergency
when paired with the primary fuel additive of the present
invention.
[0036] Suitable secondary fuel additives may be classified as
aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted
poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides,
Mannich reaction products, polyalkylphenoxyaminoalkanes, nitro and
amino aromatic esters of polyalkylphenoxyalkanols, and
nitrogen-containing carburetor/injector detergents. Each class of
secondary fuel additive will be described in more detail
herein.
[0037] In particular, the aliphatic hydrocarbyl-substituted amines
employed in the present invention may be straight or branched chain
hydrocarbyl-substituted amines having at least one basic nitrogen
and wherein the hydrocarbyl group has a number average molecular
weight of about 700 to 3,000. Specific examples of aliphatic
hydrocarbyl-substituted amines include polyisobutenyl amines and
polyisobutyl amines. These amines can be derived as monoamines or
polyamines. Preparation of aliphatic amines are generally known and
described in detail in U.S. Pat. Nos. 3,438,757; 3,565,804;
3,574,576; 3,848,056; 3,960,515; 4,832,702; and 6,203,584, all of
which are hereby incorporated by reference.
[0038] In particular, the hydrocarbyl-substituted
poly(oxyalkylene)amines employed in the present invention (also
referred to as "polyether amines") may include hydrocarbyl
poly(oxyalkylene)amines (monoamines or polyamines) wherein the
hydrocarbyl group contains from about 1 to about 30 carbon atoms.
The number of oxyalkylene units can range from about 5 to about
100. The amine moiety is derived from ammonia, primary alkyl or
secondary dialkyl monoamine, or polyamine having a terminal amino
nitrogen atom. The oxyalkylene moiety may be oxypropylene or
oxybutylene or a mixture thereof. Hydrocarbyl-substituted
poly(oxyalkylene)amines are described in U.S. Pat. Nos. 6,217,624,
and 5,112,364, which are hereby incorporated herein by reference.
Specific examples of hydrocarbyl-substituted
poly(oxyalkylene)monoamine include alkylphenyl
poly(oxyalkylene)monoamine wherein the poly(oxyalkylene) moiety
contains oxypropylene units or oxybutylene units or mixtures of
oxypropylene and oxybutylene units. The alkyl group on the
alkylphenyl moiety is a straight or branched-chain alkyl of about 1
to about 24 carbon atoms. A preferred alkylphenyl moiety is
tetrapropenylphenyl where the alkyl group is a branched-chain alkyl
of 12 carbon atoms derived from a propylene tetramer.
[0039] More particularly, additional hydrocarbyl-substituted
poly(oxyalkylene)amines include hydrocarbyl-substituted
poly(oxyalkylene)aminocarbamates disclosed in U.S. Pat. Nos.
4,288,612; 4,236,020; 4,160,648; 4,191,537; 4,270,930; 4,233,168;
4,197,409; 4,243,798 and 4,881,945, which are hereby incorporated
by reference. These hydrocarbyl poly(oxyalkylene)aminocarbamates
contain at least one basic nitrogen atom and have an average
molecular weight of about 500 to 10,000, preferably about 500 to
5,000, and more preferably about 1,000 to 3,000. A preferred
aminocarbamate is alkylphenyl poly(oxybutylene)aminocarbamate
wherein the amine moiety is derived from ethylene diamine or
diethylene triamine.
[0040] In particular, the hydrocarbyl-substituted succinimides
employed in the present invention include polyalkyl and polyalkenyl
succinimides wherein the polyalkyl or polyalkenyl group has an
average molecular weight of about 500 to 5,000, and preferably
about 700 to 3,000. The hydrocarbyl-substituted succinimides are
typically prepared by reacting a hydrocarbyl-substituted succinic
anhydride with an amine or polyamine having at least one reactive
hydrogen bonded to an amine nitrogen atom. Preferred
hydrocarbyl-substituted succinimides include polyisobutenyl and
polyisobutanyl succinimides, and derivatives thereof.
Hydrocarbyl-substituted succinimides are described in U.S. Pat.
Nos. 5,393,309; 5,588,973; 5,620,486; 5,916,825; 5,954,843;
5,993,497; and 6,114,542, and British Patent No. 1,486,144, all of
which are hereby incorporated herein by reference.
[0041] In particular, the Mannich reaction products employed in the
present invention include products typically obtained from Mannich
condensation of a high molecular weight alkyl-substituted
hydroxyaromatic compound, an amine containing at least one reactive
hydrogen, and an aldehyde. The high molecular weight
alkyl-substituted hydroxyaromatic compounds are preferably
polyalkylphenols, such as polypropylphenol and polybutylphenol,
especially polyisobutylphenol, wherein the polyakyl group has an
average molecular weight of about 600 to 3,000. The amine reactant
is typically a polyamine, such as alkylene polyamines, especially
ethylene or polyethylene polyamines, for example, ethylene diamine,
diethylene triamine, triethylene tetramine, and the like. The
aldehyde reactant is generally an aliphatic aldehyde, such as
formaldehyde, including paraformaldehyde and formalin, and
acetaldehyde. A preferred Mannich reaction product is obtained by
condensing a polyisobutylphenol with formaldehyde and diethylene
triamine, wherein the polyisobutyl group has an average molecular
weight of about 1,000. The Mannich reaction products suitable for
use in the present invention are described, for example, in U.S.
Pat. Nos. 4,231,759 and 5,697,988, the disclosures of each of which
are incorporated herein by reference.
[0042] A still further class of detergent additive suitable for use
in the present invention are polyalkylphenoxyaminoalkanes.
Preferred polyalkylphenoxyaminoalkanes include those having the
following formula:
##STR00001##
wherein R.sub.5 is a polyalkyl group having an average molecular
weight in the range of about 600 to 5,000; R.sub.6 and R.sub.7 are
independently hydrogen or lower alkyl having 1 to 6 carbon atoms;
and A is amino, N-alkyl amino having about 1 to about 20 carbon
atoms in the alkyl group, N,N-dialkyl amino having about 1 to about
20 carbon atoms in each alkyl group, or a polyamine moiety having
about 2 to about 12 amine nitrogen atoms and about 2 to about 40
carbon atoms. The polyalkylphenoxyaminoalkanes of Formula II above
and their preparations are described in detail in U.S. Pat. No.
5,669,939, which is hereby incorporated herein by reference.
[0043] Certain detergent mixtures may be particularly useful as
secondary additives in accordance with the present invention.
[0044] In some embodiments, mixtures of
polyalkylphenoxyaminoalkanes and poly(oxyalkylene)amines may be
employed. These mixtures are described in detail in U.S. Pat. No.
5,851,242, which is hereby incorporated by reference.
[0045] In some embodiments, mixtures of nitro and amino aromatic
esters of polyalkylphenoxyalkanols may be employed. Preferred nitro
and amino aromatic esters of polyalkylphenoxyalkanols include those
having the formula:
##STR00002##
wherein: R.sub.8 is nitro or --(CH.sub.2)--NR.sub.13R.sub.14,
wherein R.sub.13 and R.sub.14 are independently hydrogen or lower
alkyl having 1 to 6 carbon atoms; R.sub.9 is hydrogen, hydroxy,
nitro or --NR.sub.15R.sub.16, wherein R.sub.15 and R.sub.16 are
independently hydrogen or lower alkyl having 1 to 6 carbon atoms;
R.sub.10 and R.sub.11 are independently hydrogen or lower alkyl
having 1 to 6 carbon atoms; and R.sub.12 is a polyalkyl group
having an average molecular weight in the range of about 450 to
5,000. The aromatic esters of polyalkylphenoxyalkanols shown in
Formula III above and their preparations are described in detail in
U.S. Pat. No. 5,618,320, which is hereby incorporated herein by
reference.
[0046] Mixtures of nitro and amino aromatic esters of
polyalkylphenoxyalkanols and hydrocarbyl-substituted
poly(oxyalkylene)amines may also be employed in the present
invention. These mixtures are described in detail in U.S. Pat. No.
5,749,929, which is hereby incorporated by reference. Preferred
hydrocarbyl-substituted poly(oxyalkylene)amines which may be
employed as detergent additives in the present invention include
those having the following formula:
##STR00003##
wherein: R.sub.17 is a hydrocarbyl group having from about 1 to
about 30 carbon atoms; R.sub.18 and R.sub.19 are each independently
hydrogen or lower alkyl having about 1 to about 6 carbon atoms and
each R.sub.18 and R.sub.19 is independently selected in each
--O--CHR.sub.18--CHR.sub.19-- unit; m is from about 5 to about 100;
B is amino, N-alkyl amino having about 1 to about 20 carbon atoms
in the alkyl group, N,N-dialkyl amino having about 1 to about 20
carbon atoms in each alkyl group, or a polyamine moiety having
about 2 to about 12 amine nitrogen atoms and about 2 to about 40
carbon atoms; and m is an integer from about 5 to about 100. The
hydrocarbyl-substituted poly(oxyalkylene)amines of Formula IV above
and their preparations are described in detail in U.S. Pat. No.
6,217,624, which is hereby incorporated by reference. The
hydrocarbyl-substituted poly(oxyalkylene)amines of Formula IV are
preferably utilized either by themselves or in combination with
other detergent additives, particularly with the
polyalkylphenoxyaminoalkanes or the nitro and amino aromatic esters
of polyalkylphenoxyalkanols. More preferably, the detergent
additives employed in the present invention will be combinations of
the hydrocarbyl-substituted poly(oxyalkylene)amines with the nitro
and amino aromatic esters of polyalkylphenoxyalkanols. A
particularly preferred hydrocarbyl-substituted
poly(oxyalkylene)amine detergent additive is dodecylphenoxy
poly(oxybutylene)amine and a particularly preferred combination of
detergent additives is the combination of dodecylphenoxy
poly(oxybutylene)amine and 4-polyisobutylphenoxyethyl
para-aminobenzoate.
[0047] Another class of detergent additive suitable for use in the
present invention include nitrogen-containing carburetor/injector
detergents. The carburetor/injector detergent additives are
typically low molecular weight compounds having a number average
molecular weight of about 100 to about 600 and possessing at least
one polar moiety and at least one non-polar moiety. The non-polar
moiety is typically a linear or branched-chain alkyl or alkenyl
group having about 6 to about 40 carbon atoms. The polar moiety is
typically nitrogen-containing. Typical nitrogen-containing polar
moieties include amines (for example, as described in U.S. Pat. No.
5,139,534 and PCT International Publication No. WO 90/10051), ether
amines (for example, as described in U.S. Pat. No. 3,849,083 and
PCT International Publication No. WO 90/10051), amides, polyamides
and amide-esters (for example, as described in U.S. Pat. Nos.
2,622,018; 4,729,769; and 5,139,534; and European Patent
Publication No. 149,486), imidazolines (for example, as described
in U.S. Pat. No. 4,518,782), amine oxides (for example, as
described in U.S. Pat. Nos. 4,810,263 and 4,836,829), hydroxyamines
(for example, as described in U.S. Pat. No. 4,409,000), and
succinimides (for example, as described in U.S. Pat. No.
4,292,046). Each of these references are hereby incorporated by
reference.
[0048] Each secondary fuel additive can be present in about 50 ppm
to about 2500 ppm (such as 100 to 2000, 200 to 1500, 300 to 1000
and the like) by weight of the fuel composition. More preferably,
the secondary fuel additive is present in about 50 ppm to about
1000 ppm by weight of the fuel composition.
[0049] Other Additives
[0050] The fuel composition may comprise other generally known fuel
additives. Suitable examples include, but are not limited to,
antioxidants, metal deactivators, demulsifiers, oxygenates,
antiknock agents, dispersants and other detergents. In diesel fuel,
other well-known additives can be employed such as pour point
depressants, flow improvers, and the like.
[0051] Each of the foregoing additives, when used, is used at a
functionally effective amount to impart the desired properties to
the fuel composition. Generally, the concentration of each of these
additives, when used, may range, unless otherwise specified, from
about 0.001 to about 20 wt. %, such as about 0.01 to about 10 wt.
%.
[0052] Concentrate
[0053] The compounds of the present disclosure may be formulated as
a concentrate using an inert stable oleophilic (i.e., soluble in
hydrocarbon fuel) organic solvent boiling in a range of 65.degree.
C. to 205.degree. C. An aliphatic or an aromatic hydrocarbon
solvent may be used, such as benzene, toluene, xylene, or
higher-boiling aromatics or aromatic thinners. Aliphatic alcohols
containing 2 to 8 carbon atoms, such as ethanol, isopropanol,
methyl isobutyl carbinol, n-butanol and the like, in combination
with the hydrocarbon solvents are also suitable for use with the
present additives. In the concentrate, the amount of the additive
may range from 10 to 70 wt % (e.g., 20 to 40 wt %).
[0054] The following examples are intended to be non-limiting.
EXAMPLES
[0055] Table 1 below summarizes the additives used to test injector
fouling and/or deposit control performance. Additives used in the
following tests include isotridecyloxypropylamine (Example 1), and
polyoxybutylene amine (Example 2). Base Fuel is unadditized
gasoline composition.
TABLE-US-00001 TABLE 1 Name Ex. 1 isotridecyloxypropylamine Ex. 2
Polyoxybutylene amine
[0056] Example 1 was blended in gasoline and tested for their
ability to mitigate DISI injector fouling in a test vehicle using
the test method described herein. A 2017 V W Jetta SE equipped with
1.4 L turbocharged DISI 4-cylinder gasoline was the test vehicle
used in this Example.
[0057] FIG. 1 illustrates engine speed and load test conditions
observed during a vehicle drive cycle. The vehicle drive cycle is
based on 10 hills extracted from the transient phase of the
Environmental Protection Agency (EPA) Urban Dynamometer Drive
Schedule (UDDS) with additional idle periods added. Total drive
cycle is 20 minutes in duration and the overall test duration is
2,000-miles.
[0058] Additive testing is conducted in a "keep clean"
configuration which starts with a clean injector and combustion
chamber. This test configuration evaluates the ability of a given
deposit control additive to keep the injector and combustion
chamber clean over the duration of the test.
[0059] The test fuel samples were formulated with the target
deposit control additive. Three injector "keep clean" tests were
performed: (i) two tests using the unadditized base fuel and (ii)
one test using the same base fuel as in (i) blended with 200 ppmw
of Example 1. Injector fuel restriction (average) after the
designated drive cycles are summarized in Table 2 below.
[0060] As shown, the injector fuel restriction substantially
decreased during additized fuel use as compared to during
nonadditized fuel use. Injector fuel restriction measures the
decrease in fuel flow from the injector, representing the presence
of deposits in the injector orifices. Injector restriction can
force the engine controller to make additional control adjustments
to maintain proper engine fuel delivery, and the presence of
deposits in the injector orifices can impact fuel mixing, leading
to decreased engine performance and increased particulate
emissions. Injector face images of each formulation after
completion of test are shown in FIG. 2 and correspond to Table
2.
TABLE-US-00002 TABLE 2 Fuel Sample Average Tested injector Pulse
Width 1.5 ms 2.5 ms 3.5 ms 4.5 ms Base fuel 1.79 1.53 1.39 1.61
Base fuel 2.18 1.98 1.67 1.54 Base fuel + 200 ppmw Ex 1 0.34 0.44
0.56 0.71
[0061] A test engine was also used to evaluate PM emissions of
Example 1. A 2016 BMW B480 DISI 2.0 L 16-valve turbocharged engine
was used in this test.
[0062] The engine drive cycle is 360 s in duration with engine
speeds ranging from idle to 3000-RPM, and load varying up to
100-Nm. The overall test duration is 96 hours. FIG. 3 illustrates
engine speed and load test conditions.
[0063] PM measurements were made in the engine test stand using an
AVL Micro Soot Sensor (MSS). The MSS provides a continuous,
fast-response measurement of solid particulate mass and correlates
well with the traditional, gravimetric method of PM
measurement.
[0064] In the PM emissions trace shown in FIG. 4 (a small 2000
second segment of the larger test), one can observe how quickly PM
emissions rise and fall as engine conditions change. In order to
provide a useful metric for these data, one can look toward
official measurement methodologies used in regulatory vehicle
emissions certification (e.g. U.S. Federal Test Procedure, or FTP).
In these cases, regulatory agencies will simply report the sum
total quantity of emissions from the vehicle tailpipe over an
entire drive cycle. Applying a similar strategy to the PM dataset,
we integrate PM emissions over the course of one test drive cycle.
This integration is then repeated for each drive cycle and results
in a PM emissions trendline over the entirety of the test
duration.
[0065] FIGS. 5A-5C illustrate the results of PM emissions
trendlines (96 hour test) for fuel compositions with 150 ppmw of
Example 2 (FIG. 5A), with 150 ppmw of Example 2 and 150 ppmw of
Example 1 (FIG. 5B), and with 150 ppmw of Example 2 and 750 ppmw of
Example 1 (FIG. 5C).
[0066] FIGS. 6A-6C illustrate the results of the PM emissions
trendlines (96 hour test) for fuel compositions with 2000 ppmw of
Example 3 (FIG. 6A), with 2000 ppmw of Example 2 and 150 ppmw of
Example 1 (FIG. 6B), and with 2000 ppmw of Example 2 and 750 ppmw
of Example 1 (FIG. 6C).
[0067] FIGS. 7A-7C and FIGS. 8A-8C illustrate results of direct
injection spark-ignition (DISI) rig injector flow tests. These
graphs show percent restriction relative to clean injector flow for
various pulse widths (1.5 ms, 2.5 ms, 3.5 ms, and 4.5 ms) at 100
bar injection pressure. The samples tested include fuel
compositions with 150 ppmw of Example 2 (FIG. 7A), with 150 ppmw of
Example 2 and 150 ppmw of Example 1 (FIG. 7B), and with 150 ppmw of
Example 2 and 750 ppmw of Example 1 (FIG. 7C). The samples also
include fuel compositions with 2000 ppmw of Example 2 (FIG. 8A),
with 2000 ppmw of Example 2 and 150 ppmw of Example 1 (FIG. 8B),
and with 2000 ppmw of Example 2 and 750 ppmw of Example 1 (FIG.
8C).
[0068] FIGS. 9A-9C show injector face images that were taken after
end of vehicle or engine test (prior to flow tests) corresponding
to samples containing fuel compositions with 150 ppmw of Example 2
(FIG. 9A), with 150 ppmw of Example 2 and 150 ppmw of Example 1
(FIG. 9B), and with 150 ppmw of Example 2 and 750 ppmw of Example 1
(FIG. 9C).
[0069] FIGS. 10A-10C show injector face images that were taken
after end of vehicle or engine test (prior to flow tests)
corresponding to samples containing fuel compositions with 2000
ppmw of Example 2 (FIG. 10A), with 2000 ppmw of Example 2 and 150
ppmw of Example 1 (FIG. 10B), and with 2000 ppmw of Example 2 and
750 ppmw of Example 1 (FIG. 10C).
[0070] FIG. 11A shows average injector tip deposit volume
(mm.sup.3) for fuel compositions with 150 ppmw of Example 2 (left
bar), with 150 ppmw of Example 2 and 150 ppmw of Example 1 (middle
bar), and with 150 ppmw of Example 2 and 750 ppm of Example 1
(right bar). FIG. 11B shows average injector tip deposit volume
(mm.sup.3) for fuel compositions with 2000 ppmw of Example 2 (left
bar), with 2000 ppmw of Example 2 and 150 ppmw of Example 1 (middle
bar), and 2000 ppmw of Example 2 and 750 ppmw of Example 1 (right
bar). These measurements were taken end of vehicle or engine test
(prior to flow tests).
[0071] Table 3 below summarizes samples that were tested and rated
for anti-corrosion property using NACE TM0172 standard test method.
Base fuel is unadditized fuel. FIG. 12 provides visual confirmation
of the anti-corrosion test.
TABLE-US-00003 TABLE 3 NACE Corrosion in ASTM Type II Water Samples
% corrosion Rating Base fuel (trial 1) 70.68 D Base fuel (trial 2)
74.03 D Base fuel + 400 ppmw of 15.69 B Example 1 + 350 ppmw of
Example 2 (trial 1) Base fuel + 400 ppmw of 3.97 B+ Example 1 + 350
ppmw of Example 2 (trial 2)
[0072] All documents described herein are incorporated by reference
herein, including any priority documents and/or testing procedures
to the extent they are not inconsistent with this text. As is
apparent from the foregoing general description and the specific
embodiments, while forms of the present disclosure have been
illustrated and described, various modifications can be made
without departing from the spirit and scope of the present
disclosure. Accordingly, it is not intended that the present
disclosure be limited thereby.
[0073] For the sake of brevity, only certain ranges are explicitly
disclosed herein. However, ranges from any lower limit may be
combined with any upper limit to recite a range not explicitly
recited, as well as, ranges from any lower limit may be combined
with any other lower limit to recite a range not explicitly
recited, in the same way, ranges from any upper limit may be
combined with any other upper limit to recite a range not
explicitly recited. Additionally, within a range includes every
point or individual value between its end points even though not
explicitly recited. Thus, every point or individual value may serve
as its own lower or upper limit combined with any other point or
individual value or any other lower or upper limit, to recite a
range not explicitly recited.
[0074] Likewise, the term "comprising" is considered synonymous
with the term "including." Likewise whenever a composition, an
element or a group of elements is preceded with the transitional
phrase "comprising," it is understood that we also contemplate the
same composition or group of elements with transitional phrases
"consisting essentially of," "consisting of," "selected from the
group of consisting of," or "is" preceding the recitation of the
composition, element, or elements and vice versa.
[0075] The terms "a" and "the" as used herein are understood to
encompass the plural as well as the singular.
[0076] Various terms have been defined above. To the extent a term
used in a claim is not defined above, it should be given the
broadest definition persons in the pertinent art have given that
term as reflected in at least one printed publication or issued
patent. Furthermore, all patents, test procedures, and other
documents cited in this application are fully incorporated by
reference to the extent such disclosure is not inconsistent with
this application and for all jurisdictions in which such
incorporation is permitted.
[0077] The foregoing description of the disclosure illustrates and
describes the present disclosure. Additionally, the disclosure
shows and describes only the preferred embodiments but, as
mentioned above, it is to be understood that the disclosure is
capable of use in various other combinations, modifications, and
environments and is capable of changes or modifications within the
scope of the concept as expressed herein, commensurate with the
above teachings and/or the skill or knowledge of the relevant art.
While the foregoing is directed to embodiments of the present
disclosure, other and further embodiments of the disclosure may be
devised without departing from the basic scope thereof, and the
scope thereof is determined by the claims that follow.
[0078] It is understood that when combinations, subsets, groups,
etc. of elements are disclosed (e.g., combinations of components in
a composition, or combinations of steps in a method), that while
specific reference of each of the various individual and collective
combinations and permutations of these elements may not be
explicitly disclosed, each is specifically contemplated and
described herein.
[0079] The embodiments described hereinabove are further intended
to explain best modes known of practicing it and to enable others
skilled in the art to utilize the disclosure in such, or other,
embodiments and with the various modifications required by the
particular applications or uses. Accordingly, the description is
not intended to limit it to the form disclosed herein. Also, it is
intended that the appended claims be construed to include
alternative embodiments.
* * * * *