U.S. patent application number 14/048845 was filed with the patent office on 2015-04-09 for alkoxylated quaternary ammonium salts and fuels containing them.
This patent application is currently assigned to Afton Chemical Corporation. The applicant listed for this patent is Afton Chemical Corporation. Invention is credited to Xinngao FANG, Scott D. SCHWAB.
Application Number | 20150096516 14/048845 |
Document ID | / |
Family ID | 51663056 |
Filed Date | 2015-04-09 |
United States Patent
Application |
20150096516 |
Kind Code |
A1 |
FANG; Xinngao ; et
al. |
April 9, 2015 |
ALKOXYLATED QUATERNARY AMMONIUM SALTS AND FUELS CONTAINING THEM
Abstract
A fuel additive and its preparation for a engine, a fuel
containing the additive, a fuel additive concentrate, a method for
improving performance of fuel injectors and a method for cleaning
fuel injectors for an engine. The fuel additive includes a
quaternary ammonium salt derived from a reaction of a hydrocarbyl
substituted anhydride, a tertiary amine and a hydroxyl-containing
epoxide, wherein the tertiary amine is devoid of primary and
secondary amino groups.
Inventors: |
FANG; Xinngao; (Midlothian,
VA) ; SCHWAB; Scott D.; (Richmond, VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Afton Chemical Corporation |
Richmond |
VA |
US |
|
|
Assignee: |
Afton Chemical Corporation
Richmond
VA
|
Family ID: |
51663056 |
Appl. No.: |
14/048845 |
Filed: |
October 8, 2013 |
Current U.S.
Class: |
123/1A ; 44/419;
554/52 |
Current CPC
Class: |
C10L 10/04 20130101;
C10L 10/06 20130101; F02B 77/00 20130101; C10L 2200/0446 20130101;
C07C 237/16 20130101; C10L 2200/0423 20130101; C10L 1/224 20130101;
C10L 1/221 20130101; C10L 2230/086 20130101; C10L 2200/0476
20130101; C07C 231/14 20130101; C10L 1/238 20130101 |
Class at
Publication: |
123/1.A ; 44/419;
554/52 |
International
Class: |
C10L 1/224 20060101
C10L001/224; C07C 231/14 20060101 C07C231/14; F02B 77/00 20060101
F02B077/00; C07C 237/16 20060101 C07C237/16 |
Claims
1. A fuel additive for a fuel injected engine comprising a
quaternary ammonium salt derived from a reaction of a hydrocarbyl
substituted anhydride, a tertiary amine and a hydroxyl-containing
epoxide selected from the group consisting of hydroxymethyl
cyclohexene oxide, butanediol monoglycidyl ether, propanediol
monoglycidyl ether, hexanediol monoglycidyl ether,
cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl
ether, glycerol diglycidyl ether, pentaerythritol triglycidyl
ether, glycidol, 3-glycidyloxybenzyl alcohol, and combinations of
two or more of the foregoing, wherein the tertiary amine is devoid
of primary and secondary amino groups.
2-3. (canceled)
4. The fuel additive of claim 1, wherein the reaction is conducted
without the addition of a carboxylic acid or an acid containing
compound to the reactants.
5. The fuel additive of claim 1, wherein the hydrocarbyl group of
the hydrocarbyl substituted anhydride is selected from
C.sub.9-C.sub.30 alkenyl groups and polyisobutenyl groups.
6. The fuel additive of claim 1, wherein the amine is selected from
the group consisting of oleylamido propyl dimethylamine, and
dodecyldimethylamine.
7. The fuel additive of claim 1, wherein the tertiary amine
comprises compounds of the formula ##STR00004## wherein each of
R.sup.10, R.sup.11 and R.sup.14 is selected from hydrocarbyl groups
containing from 1 to 50 carbon atoms, R.sup.9 is selected from
hydrogen or a hydrocarbyl group, R.sup.12, and R.sup.13 may be
independently selected from a hydrocarbyl group, x may range from 1
to 6, y may be 0 or 1, z may be 1 to 6, and n may range from 1 to
6.
8. A fuel composition comprising from about 5 to about 200 ppm of
the fuel additive of claim 1 based on a total weight of the fuel
composition.
9. A diesel fuel composition comprising from about 10 to about 200
ppm of the fuel additive of claim 1 based on a total weight of the
fuel composition, wherein the fuel composition exhibits injector
cleaning attributes and full water recovery and an interface rating
of 1b in a demulsibility test according to ASTM D-1094.
10. A method of improving the injector performance of a direct fuel
injected engine comprising operating the engine on a fuel
composition comprising a major amount of fuel and from about 5 to
about 200 ppm by weight based on a total weight of the fuel
composition of a quaternary ammonium salt derived from a reaction
of a hydrocarbyl substituted anhydride, a tertiary amine and a
hydroxyl-containing epoxide selected from the group consisting of
hydroxymethyl cyclohexene oxide, butanediol monoglycidyl ether,
propanediol monoglycidyl ether, hexanediol monoglycidyl ether,
cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl
ether, glycerol diglycidyl ether, pentaerythritol triglycidyl
ether, glycidol, 3-glycidyloxybenzyl alcohol, and combinations of
two or more of the foregoing, wherein the tertiary amine is devoid
of primary and secondary amino groups.
11. The method of claim 10, wherein the engine comprises a direct
fuel injected diesel engine.
12. The method of claim 10, wherein the engine comprises a direct
fuel injected gasoline engine.
13. The method of claim 10, wherein the tertiary amine comprises an
amido amine derived from an acid compound having from about 1 to
about 54 carbon atoms.
14. (canceled)
15. The method of claim 10, wherein the fuel composition contains
from about 10 to about 50 ppm of the quaternary ammonium salt based
on a total weight of the fuel composition.
16. A method of operating a direct fuel injected diesel engine
comprising combusting in the engine a fuel composition comprising a
major amount of fuel and from about 5 to about 200 ppm by weight
based on a total weight of the fuel composition of a quaternary
ammonium salt derived from a reaction of a hydrocarbyl substituted
anhydride, a tertiary amine and a hydroxyl-containing epoxide
selected from the group consisting of hydroxymethyl cyclohexene
oxide, butanediol monoglycidyl ether, propanediol monoglycidyl
ether, hexanediol monoglycidyl ether, cyclohexanedimethanol
glycidyl ether, trimethylolpropane diglycidyl ether, glycerol
diglycidyl ether, pentaerythritol triglycidyl ether, glycidol,
3-glycidyloxybenzyl alcohol, and combinations of two or more of the
foregoing, wherein the tertiary amine is devoid of primary and
secondary amino groups.
17. (canceled)
18. A method for making a quaternary ammonium salt for use as a
fuel detergent comprising combining, as reactants, a hydrocarbyl
substituted anhydride, a tertiary amine and a hydroxyl-containing
epoxide selected from the group consisting of hydroxymethyl
cyclohexene oxide, butanediol monoglycidyl ether, propanediol
monoglycidyl ether, hexanediol monoglycidyl ether,
cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl
ether, glycerol diglycidyl ether, pentaerythritol triglycidyl
ether, glycidol, 3-glycidyloxybenzyl alcohol, and combinations of
two or more of the foregoing, and reacting the reactants under
conditions sufficient to form a quaternary ammonium salt, wherein
the tertiary amine is devoid of primary and secondary amino
groups.
19. The method of claim 18, wherein the combining and reaction
steps are conducted without the addition of a carboxylic acid or an
acid containing compound to the reactants.
20-21. (canceled)
Description
TECHNICAL FIELD
[0001] The disclosure is directed to a fuel additive and to fuels
that include the additive that are useful for improving the
performance of fuel injected engines. In particular the disclosure
is directed to an alkoxylated quaternary ammonium salt fuel
additive that is effective to enhance the performance of fuel
injectors for gasoline and diesel engines.
BACKGROUND AND SUMMARY
[0002] It is well known that liquid fuel contains components that
can degrade during engine operation and form deposits. Such
deposits can lead to incomplete combustion of the fuel resulting in
higher emissions and poorer fuel economy. Detergents are well known
additives in liquid fuels to help minimize deposit formation. As
the dynamics and mechanics of an engine continually advance, the
requirements of the fuels and additives must evolve to keep up with
these engine advancements. For example, today's engines have
injector systems that have smaller tolerances and operate at higher
pressure to enhance fuel spray to the compression or combustion
chamber. Deposit prevention and reduction has become critical to
optimal operation, and therefore there is a need for detergents
capable of providing acceptable performance in a liquid fuel to
promote optimal engine operation.
[0003] Furthermore, there is a dramatic difference between indirect
fuel injected diesel engines, and more modern high pressure common
rail (HPCR), direct fuel injected diesel engines. Also, low sulfur
diesel fuels and ultra low sulfur diesel fuels are now common in
the marketplace for such engines. A "low sulfur" diesel fuel means
a fuel having a sulfur content of 500 ppm by weight or less based
on a total weight of the fuel. An "ultra low sulfur" diesel fuel
(ULSD) means a fuel having a sulfur content of 15 ppm by weight or
less based on a total weight of the fuel. Fuel injectors in an HPCR
engine perform at much higher pressures and temperatures compared
to older style engines and fuel injection systems. The combination
of low sulfur or ULSD and HPCR engines have resulted in a change to
the type of injector deposits and frequency of formation of
injector deposits now being found in the marketplace.
[0004] Hence, fuel compositions for direct fuel injected engines
often produce undesirable deposits in the internal engine surfaces
and fuel filters. Accordingly, improved compositions that can
prevent deposit build up, maintaining "as new" cleanliness for the
vehicle life are desired. Ideally, the same composition that can
clean up dirty fuel injectors restoring performance to the previous
"as new" condition would be equally desirable and valuable in the
attempt to reduce air borne exhaust emissions and to improve the
power performance of the engines.
[0005] It is known to use certain polyisobutenyl succinimide
(PIBSI)-derived quaternary ammonium salt detergents as additives in
fuel compositions to promote optimal engine operation, for example,
increased fuel economy, better vehicle drivability, reduced
emissions and less engine maintenance by reducing, minimizing and
controlling deposit formation. Such quaternized detergents are
typically derived from traditional PIBSI fuel additive compounds
that have pendant tertiary amine sites which can be alkylated, i.e.
quaternized, by a quaternizing agent, such as propylene oxide.
Examples of such reactions and reaction products are included in
U.S. Pat. No. 8,147,569.
[0006] A new improved class of quaternary ammonium salt detergents
derived from polyisobutenyl succinamides and/or esters have also
been disclosed. Such additives are claimed to be more thermally
stable than the PIBSI-derived quaternary ammonium salt detergents
and may be manufactured by a less energy-intensive process.
Examples of such reactions and reaction products are included in
U.S. Publication No. 2012/0138004.
[0007] Quaternary ammonium salt detergents often require the use of
flammable and dangerous epoxides such as propylene oxide and
further require the use of specialized and expensive pressure
vessels for their production. The alkoxylation step requires a
carboxylic acid as proton donor. The resulting carboxylate may lead
to deposit formation and other issues related to carboxylate salts
being present in the additive and fuel.
[0008] In addition, the polyisobutenyl succinamide and/or ester
intermediates tend to be very viscous and difficult to handle
during the manufacturing process. The reaction products often
contain varying amounts of polyisobutenyl succinimides rendering it
difficult to charge a correct amount of epoxide and or acid to the
reaction mixture.
[0009] Lastly, conventional quaternized PIB/amine ammonium salts
tend to negatively impact the demulsibility of fuels such as diesel
fuels.
[0010] The present invention relates to a new class of alkoxylated
quaternary ammonium detergents which offer significant improvements
over the prior art polysiobutylene succinimide, amide and or ester
derived PIB/amine quaternary ammonium salts. The process requires
no specialized and/or expensive pressure reactors. The resulting
quaternary salts not only afford improved detergency performance
but also provide improved demulsibility.
[0011] In accordance with the disclosure, exemplary embodiments
provide a fuel additive and its preparation for a engine, a fuel
containing the additive, a fuel additive concentrate, a method for
improving performance of fuel injectors and a method for cleaning
fuel injectors for an engine. The fuel additive includes a
quaternary ammonium salt derived from a reaction of a hydrocarbyl
substituted anhydride, a tertiary amine and a hydroxyl-containing
epoxide, wherein the tertiary amine is devoid of primary and
secondary amino groups. The fuel additive concentrate comprises the
fuel additive and one or more components and/or solvents.
[0012] Another embodiment of the disclosure provides a method of
improving the injector performance of a direct fuel injected
engine. The method includes operating the engine on a fuel
composition containing a major amount of fuel and from about 5 to
about 200 ppm by weight based on a total weight of the fuel
composition of a quaternary ammonium salt derived from a reaction
of a hydrocarbyl substituted anhydride, a tertiary amine and a
hydroxyl-containing epoxide, wherein the tertiary amine is devoid
of primary and secondary amino groups.
[0013] A further embodiment of the disclosure provides a method of
operating a direct fuel injected diesel engine. The method includes
combusting in the engine a fuel composition containing a major
amount of fuel and from about 5 to about 200 ppm by weight based on
a total weight of the fuel composition of a quaternary ammonium
salt from a reaction of a hydrocarbyl substituted anhydride, a
tertiary amine and a hydroxyl-containing epoxide, wherein the
tertiary amine is devoid of primary and secondary amino groups.
[0014] An additional embodiment of the disclosure provides a method
for making a quaternary ammonium salt for use as a fuel detergent.
The method includes combining, as reactants, a hydrocarbyl
substituted anhydride, a tertiary amine and a hydroxyl-containing
epoxide, and reacting the reactants under conditions sufficient to
form a quaternary ammonium salt. The tertiary amine is devoid of
primary and secondary amino groups.
[0015] An advantage of the fuel additive described herein is that
the additive may not only reduce the amount of deposits forming on
fuel injectors and be effective to clean up dirty fuel injectors
sufficient to provide improved power recovery to the engine, but
the additive may also unexpectedly enhance the demulsibility of the
fuel composition.
[0016] Additional embodiments and advantages of the disclosure will
be set forth in part in the detailed description which follows,
and/or can be learned by practice of the disclosure. It is to be
understood that both the foregoing general description and the
following detailed description are exemplary and explanatory only
and are not restrictive of the disclosure, as claimed.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0017] The fuel additive component of the present application may
be used in a minor amount in a major amount of fuel and may be
added to the fuel directly or added as a component of an additive
concentrate to the fuel. A particularly suitable fuel additive
component for improving the operation of internal combustion
engines may be made by reacting a tertiary amine of the formula
##STR00001##
with a hydroxyl-containing epoxide in the presence of an anhydride
to provide an alkoxylated quaternary ammonium salt, wherein each of
R.sup.1, R.sup.2, and R.sup.3 is selected from hydrocarbyl groups
containing from 1 to 200 carbon atoms. The tertiary amine may be
reacted with the hydroxyl-containing epoxide and an anhydride to
provide the quaternary ammonium salt or the tertiary amine may be
an imide-amine that is reacted with a hydroxyl-containing epoxide,
provided the imide-amine and tertiary amine are devoid of primary
and secondary amino groups. The imide-amine may be derived from a
hydrocarbyl-substituted anhydride and an amine having primary and
tertiary amino groups and being devoid of secondary amino groups. A
key feature of the disclosure is that the quaternary amine reaction
product is made in the substantial absence of added acid and/or
non-hydroxyl-containing epoxides.
[0018] Exemplary tertiary amines include, but are not limited to
dimethyl hexylamine, dimethyl octylamine, dimethyl decylamine,
dimethyl tetradecylamine, dimethyl pentadecylamine, dimethyl
hexadecylamine, dimethyl dodecylamine, dimethyl octadecylamine,
diethyl hexylamine, diethyl octylamine, diethyl decylamine, diethyl
dodecylamine, diethyl tetradecylamine, diethyl pentadecylamine,
diethyl hexadecylamine, diethyl octadecylamine, dipropyl
hexylamine, dipropyl octylamine, dipropyl decylamine, dipropyl
dodecylamine, dipropyl tetradecylamine, dipropyl pentadecylamine,
dipropyl hexadecylamine, dipropyl octadecylamine, oleylamido propyl
dimethylamine, C.sub.9-C.sub.30 alkenyl succinimide propyl dimethyl
amine, C.sub.9-C.sub.30 alkenyl succinimide propyl dimethyl amine,
polyisobutenyl succinimide propyl dimethyl amine, and a
poly-tertiary amine. In one embodiment, a tertiary amine including
diamines and polyamines may be reacted with a C.sub.1 to C.sub.54
fatty acid to form an amido amine and the amido amine may be
subsequently reacted with an anhydride and the hydroxyl-containing
epoxide to form the quaternary ammonium salt. Suitable tertiary
amido amine compounds of the formula
##STR00002##
may be used, wherein each of R.sup.10, R.sup.11 and R.sup.14 is
selected from hydrocarbyl groups containing from 1 to 50 carbon
atoms, each R.sup.9, R.sup.12, and R.sup.13 may be independently
selected from hydrogen or a hydrocarbyl group, x may range from 1
to 6, y may be 0 or 1, z may be 1 to 6, and n may range from 1 to
6. Each hydrocarbyl group R.sup.9 to R.sup.14 may independently be
linear, branched, substituted, cyclic, saturated, unsaturated, or
contain one or more hetero atoms. Suitable hydrocarbyl groups may
include, but are not limited to alkyl groups, aryl groups,
alkylaryl groups, arylalkyl groups, alkoxy groups, aryloxy groups,
amino groups, and the like. Particularly suitable hydrocarbyl
groups may be linear or branched alkyl groups.
[0019] 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: [0020] (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); [0021] (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); [0022] (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.
[0023] Despite the foregoing definition of a hydrocarbyl group, the
R.sup.1, R.sup.2, and R.sup.3 groups of the tertiary amine do not
include primary and secondary amino groups.
[0024] 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.
Hydroxyl-Containing Epoxide
[0025] A suitable epoxide may be selected from the group consisting
compounds of the formula:
##STR00003##
wherein each R is independently selected from H, OH and a C.sub.1
to C.sub.50 hydrocarbyl group, and polyepoxides, provided at least
one R includes a primary, secondary or tertiary hydroxyl group.
Non-limiting examples of suitable epoxides that may be used as
quaternizing agents may be selected from mono- and polyglycidyl
ethers of polyalcohols, such as, for example,
[0026] hydroxymethyl cyclohexene oxide,
[0027] butanediol monoglycidyl ether,
[0028] propanediol monoglycidyl ether
[0029] hexanediol monoglycidyl ether,
[0030] cyclohexanedimethanol glycidyl ether,
[0031] trimethylolpropane diglycidyl ether,
[0032] glycerol diglycidyl ether,
[0033] pentaerythritol triglycidyl ether,
[0034] glycidol,
[0035] 3-glycidyloxybenzyl alcohol, and combinations of two or more
of the foregoing.
[0036] The quaternary ammonium salts from tertiary amines and
hydroxyl-containing epoxides may be made in one stage or two
stages. The reaction may be carried out by contacting and mixing
the hydroxyl-containing epoxide with an anhydride, then contacting
and reacting the mixture with the tertiary amine. In another
process, all three reactants may be mixed together in a single
reaction vessel. In another process, a primary or secondary amine
may be first reacted with an electrophile to form a tertiary amine
or an imide, amide, or the like devoid of primary and secondary
amino groups, and then the tertiary amine is reacted with the
hydroxyl-containing epoxide and an anhydride. An important feature
of the reaction is that prior to reaction with the epoxide, the
tertiary amine is devoid of primary and secondary amino groups. In
another important feature of the disclosure is that the reaction is
conducted without the addition to the reaction mixture of a
carboxylic acid or an acid containing compound.
[0037] The reaction may be carried out at temperature ranging from
about 30.degree. to about 90.degree. C., for example from about
45.degree. to about 70.degree. C. The reaction may be conducted by
reacting any amount of tertiary amino groups to epoxy groups
sufficient to provide a quaternary ammonium compound. In one
embodiment a mole ratio of tertiary amino groups to epoxy groups
may range from about 2:1 to about 1:2. When the reaction is
completed volatiles and unreacted reagents may be removed from the
reaction product by heating the reaction product under vacuum. The
product may be diluted with mineral oil, diesel fuel, kerosene, or
an inert hydrocarbon solvent to prevent the product from being too
viscous, if necessary.
[0038] One or more additional optional compounds may be present in
the fuel additive concentrate and/or the fuel compositions of the
disclosed embodiments. For example, the fuels may contain
conventional quantities of nitrogen-containing detergents, octane
improvers cetane improvers, corrosion inhibitors, cold flow
improvers (CFPP additive), pour point depressants, solvents,
demulsifiers, lubricity additives, friction modifiers, amine
stabilizers, combustion improvers, dispersants, antioxidants, heat
stabilizers, conductivity improvers, metal deactivators, marker
dyes, organic nitrate ignition accelerators, cyclomatic manganese
tricarbonyl compounds, and the like. In some aspects, the
compositions described herein may contain about 60 weight percent
or less, or in other aspects, about 50 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, butanol, isobutanol, fatty acid alkyl ester,
dialkyl ethers, 2-ethylhexanol, and the like.
[0039] In some aspects of the disclosed embodiments, organic
nitrate ignition accelerators that include aliphatic or
cycloaliphatic nitrates in which the aliphatic or cycloaliphatic
group is saturated, and that contain up to about 12 carbons may be
used. Examples of organic nitrate ignition accelerators that may be
used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl
nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl
nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl
nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl
nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate,
nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate,
cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate,
cyclododecyl nitrate, 2-ethoxyethyl nitrate,
2-(2-ethoxyethoxyl)ethyl nitrate, tetrahydrofuranyl nitrate, and
the like. Mixtures of such materials may also be used.
[0040] Examples of suitable optional metal deactivators useful in
the compositions of the present application are disclosed in U.S.
Pat. No. 4,482,357 issued Nov. 13, 1984, 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.
[0041] When formulating the fuel compositions of this application,
the additives may be employed in amounts sufficient to reduce or
inhibit deposit formation in a fuel system or combustion chamber of
an engine and/or crankcase. In some aspects, the fuels may contain
minor amounts of the above described reaction product that controls
or reduces the formation of engine deposits, for example injector
deposits in diesel engines. For example, the fuels of this
disclosure may contain, on an active ingredient basis, an amount of
the quaternary ammonium salt in the range of about 1 mg to about
200 mg of quaternary ammonium salt per Kg of fuel, such as in the
range of about 5 mg to about 50 mg of per Kg of fuel or in the
range of from about 5 mg to about 25 mg of the quaternary ammonium
salt per Kg of fuel. 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.
[0042] The additives of the present application, including the
quaternary ammonium salt 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.
[0043] The fuels of the present application may be applicable to
the operation of gasoline and diesel engines. The engine include
both stationary engines (e.g., engines used in electrical power
generation installations, in pumping stations, etc.) and ambulatory
engines (e.g., engines used as prime movers in automobiles, trucks,
road-grading equipment, military vehicles, etc.). For example, the
fuels may include any and all gasoline grades, middle distillate
fuels, diesel fuels, biorenewable fuels, biodiesel fuel, fatty acid
alkyl ester, gas-to-liquid (GTL) fuels, 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.
[0044] Accordingly, aspects of the present application are directed
to methods for reducing the amount of injector deposits of engines
having at least one combustion chamber and one or more direct fuel
injectors in fluid connection with the combustion chamber. In
another aspect, the quaternary ammonium salts described herein or
fuel containing the quaternary ammonium salt may be combined with
polyhydrocarbyl-succinimides, -acids, -amides, -esters,
-amide/acids, -acid/esters, -Mannich compounds, polyhydrocarbyl
amines, and polyether amines.
[0045] In some aspects, the methods comprise injecting a
hydrocarbon-based fuel comprising a quaternary ammonium salt of the
present disclosure through the injectors of the engine into the
combustion chamber, and igniting the fuel. In some aspects, the
method may also comprise mixing into the fuel at least one of the
optional additional ingredients described above.
EXAMPLES
[0046] The following examples are illustrative of exemplary
embodiments of the disclosure. In these examples as well as
elsewhere in this application, all 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
[0047] A quaternary ammonium salt was prepared by a method
according to U.S. Pat. No. 8,147,569. To a mixture of PIBSI
(reaction product of polyisobutenyl succinic anhydride (PIBSA) and
dimethylaminopropyl amine (DMAPA), 1:1) (249 grams) made according
to U.S. Pat. No. 8,147,569 and aromatic solvent aromatic (70 grams)
was added acetic acid (17.3 grams), 1,2-butylene oxide (34.6
grams), isopropanol (64 grams), and 2-ethylhexanol (18 grams). The
mixture was heated at 50.degree. C. for 1 hour, then at 55.degree.
C. for 2 hours and 15 minutes, 60.degree. C. for 2 hours, and
65.degree. C. for 5 hours. Volatiles were removed under reduced
pressure at 65.degree. C. to give product as a brown viscous oil
containing the quaternary ammonium salt.
Comparative Example 2
[0048] A quaternary ammonium salt was prepared by a method
according U.S. Publication No. 2012/0138004. According to the
procedure of "preparatory material A", a mixture of PIBSA (PIB
Mn=950, 225 grams) and aromatic solvent (91 grams) was heated to
45.degree. C. DMAPA (23.4 grams) was added over 10 minutes to keep
the mixture temperature from rising above 60.degree. C. It was
found the reaction mixture was very viscous and was difficult to
stir. The mixture was stirred at 60.degree. C. for 2 hours. Then
2-ethyl hexanol (68 grams) and 1,2-butylene oxide (33.4 grams) were
added to the reaction product. The resulting mixture was heated at
55.degree. C. for 1 hour, 60.degree. C. for 1 hour, 62.5.degree. C.
for 2 hours, and 65.degree. C. for 1 hour. Volatiles were removed
under reduced pressure to give the quaternary ammonium salt product
as a brownish oil.
Inventive Example 1
[0049] A mixture of PIBSA (229 grams) and glycidol (17.4 grams) and
aromatic solvent (53 grams) was heated to 45.degree. C. for 30
minutes. Oleylamido propyl dimethylamine (86 grams) was added to
the mixture slowly to keep the temperature below 52.degree. C. Then
2-ethylhexanol (94 grams) was added to the mixture. The final
mixture was reacted at 55.degree. C. for 1 hour, then 60.degree. C.
for 2.5 hours, and 65.degree. C. for 1 hour to give product as a
viscous oil.
Inventive Example 2
[0050] A quaternary ammonium salt was prepared similarly to that of
Inventive Example 1 except that a C.sub.20-C.sub.24 alkenyl
succinic anhydride was used in place of PIBSA.
Inventive Example 3
[0051] A quaternary ammonium salt was prepared similarly to that of
Inventive Example 1 except that dodecyldimethylamine was used in
place of oleylamido propyl dimethylamine.
Inventive Example 4
[0052] A quaternary ammonium salt was prepared similarly to that of
Inventive Example 1 except that the tertiary amine used for the
reaction was the reaction product of dodecyl succinic anhydride
(DDSA) and dimethylaminopropylamine (DMAPA), and the reaction
product of DDSA and DMAPA was used in place of oleylamido propyl
dimethylamine.
Inventive Example 5
[0053] An aromatic solvent (86 grams) and PIBSI (263 grams) made
according to Comparative Example 1 was added to acetic anhydride
(26.5 grams). The mixture was heated at 36.degree. C. and glycidol
(19 grams) was added in less than 1 minute. The temperature of the
mixture rose to 55.degree. C. The mixture was then stirred at
50.degree. C. for 30 minutes. To the mixture was added
2-ethylhexanol (49 grams). The resulting mixture was reacted at
55.degree. C. for 1 hour, 60.degree. C. for 1 hour, 65.degree. C.
for 6.5 hours to give product as a brownish oil.
[0054] In the following example, an injector deposit test was
performed on a diesel engine using an industry standard diesel
engine fuel injector test, CEC F-98-08 (DW10) as described below.
Table 2 contains the results of the DW10 test conducted on a soy
methyl ester B10 diesel fuel and Table 3 contains the results of
the DW10 test conducted on a reference PC10 fuel.
Diesel Engine Test Protocol
[0055] A DW10 test that was developed by Coordinating European
Council (CEC) was used to demonstrate the propensity of fuels to
provoke fuel injector fouling and was also 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 have a Euro V classification.
[0056] 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.
[0057] 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 4000 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. The
following Table 1 provides a representation of the DW10 coking
cycle that was used to evaluate the fuel additives according to the
disclosure.
TABLE-US-00001 TABLE 1 One hour representation of DW10 coking
cycle. Engine speed Load Torque Boost air after Duration (minutes)
(rpm) (%) (Nm) Intercooler (.degree. C.) 2 1750 20 62 45 7 3000 60
173 50 2 1750 20 62 45 7 3500 80 212 50 2 1750 20 62 45 10 4000 100
* 50 2 1250 10 25 43 7 3000 100 * 50 2 1250 10 25 43 10 2000 100 *
50 2 1250 10 25 43 7 4000 100 * 50
[0058] Various fuel additives 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 with additive. 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-00002 TABLE 2 Power Additive Additives and Power recovery
% Efficiency treat rate loss % (DU - CU)/ Power Recovery (ppm by
weight) DU CU DU .times. 100 %/ppm Comparative Example -5.87 -2.93
50 0.50 1 (100 ppm) Inventive Example 1 -4.99 -1.29 74 0.74 (100
ppm) Inventive Example 2 -4.77 -1.39 71 1.42 (50 ppm)
TABLE-US-00003 TABLE 3 Power Additive Additives and Power recovery
% Efficiency treat rate loss % (DU - CU)/ Power Recovery (ppm by
weight) DU CU DU .times. 100 %/ppm Comparative Example -5.75 -0.09
98 1.30 2 (75 ppm) Inventive Example 1 -5.17 -0.47 91 1.21 (75 ppm)
Inventive Example 2 -5.53 0.99 118 1.57 (75 ppm)
[0059] In Tables 2 and 3, the "Additive Efficiency" is the percent
recovery for each part per million of additive in the fuel.
[0060] A demulsibility test according to ASTM D-1094 was conducted
on several samples in order to determine the impact on fuel
demulsibility of the reaction products in a fuel. The fuel used for
the test was an ultra low sulfur diesel (ULSD) fuel having a pH
buffered at 7 and including the additive at a treat rate of 200
ppm. The fuel also contained 10 ppm commercial polyglycol
demulsifier. The results are shown in the following table.
TABLE-US-00004 TABLE 4 Base ULSD fuel + Full Water Interface rating
Separation at 5 Fuel clarity at 5 Additive Recovery Time 1b Time at
5 minutes minutes minutes No additive 55 seconds 1 minute 1 1 1
Comparative Ex. 1 Not achieved Not achieved 2 1 1 Comparative Ex. 2
Not achieved Not achieved 2 1 1 Inventive Ex. 1 3 min. 15 sec. 4
min. 25 sec. 1b 1 1 Inventive Ex. 2 4 min. 50 sed. 5 min. 1b 1
1
[0061] It was surprisingly found that Inventive Examples 1 and 2
made with a hydroxyl substituted epoxide had superior
demulsifibility compared to Comparative Example 1 when tested
according to ASTM D-1094. Accordingly, Inventive Examples 1 and 2
not only exhibit surprisingly superior injector cleaning attributes
as shown by the power recovery in Tables 2 and 3, but also superior
demulsibility compared to Comparative Examples 1 and 2 made by the
comparative processes.
[0062] 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
[0063] 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.
[0064] 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.
* * * * *