U.S. patent application number 13/121714 was filed with the patent office on 2011-09-15 for additives to reduce metal pick-up in fuels.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. Invention is credited to Robert H. Barbour, Emma Fahey, Paul R. Stevenson.
Application Number | 20110219674 13/121714 |
Document ID | / |
Family ID | 41565924 |
Filed Date | 2011-09-15 |
United States Patent
Application |
20110219674 |
Kind Code |
A1 |
Barbour; Robert H. ; et
al. |
September 15, 2011 |
Additives to Reduce Metal Pick-Up in Fuels
Abstract
The present invention relates to fuel additives, fuel additive
compositions and fuel compositions, as well as a method for fueling
an internal combustion engine, providing reduced metal pick-up by
fuels where the compositions of the present invention contain a
hydrocarbon substituted with at least two carboxy functionalities
in the form of acids or at least one carboxy functionality in the
form of an anhydride.
Inventors: |
Barbour; Robert H.;
(Ashbourne, GB) ; Stevenson; Paul R.; (Belper,
GB) ; Fahey; Emma; (Belper, GB) |
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
41565924 |
Appl. No.: |
13/121714 |
Filed: |
October 1, 2009 |
PCT Filed: |
October 1, 2009 |
PCT NO: |
PCT/US09/59164 |
371 Date: |
May 17, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61104304 |
Oct 10, 2008 |
|
|
|
Current U.S.
Class: |
44/347 ; 44/422;
44/437; 44/451 |
Current CPC
Class: |
C10L 10/00 20130101;
C10L 1/2222 20130101; C10L 1/143 20130101; C10L 1/198 20130101;
C10L 1/2383 20130101; C10L 10/04 20130101; C10L 1/1883
20130101 |
Class at
Publication: |
44/347 ; 44/422;
44/437; 44/451 |
International
Class: |
C10L 1/232 20060101
C10L001/232; C10L 1/22 20060101 C10L001/22; C10L 1/185 20060101
C10L001/185; C10L 1/182 20060101 C10L001/182 |
Claims
1. A method of reducing the amount of oxidative metals pick-up in a
fuel composition wherein the method comprises: adding to the fuel
composition an additive comprising a hydrocarbon substituted with
at least two carboxy functionalities in the form of acids or at
least one carboxy functionality in the form an anhydride.
2. The method of claim 1 wherein the substituted hydrocarbon is a
hydrocarbyl substituted acylating agent has di-acid
functionality.
3. The method of claim 1 wherein the substituted hydrocarbon is a
succinic acylating agent.
4. The method of claim 1 wherein the oxidative metal, for which
pick-up is being reduced, is selected from the group consisting of
copper, zinc, iron, or combinations thereof.
5. The method of claim 1 wherein the hydrocarbyl group of the
substituted hydrocarbon comprises polyisobutylene.
6. The method of claim 1 wherein the substituted hydrocarbon agent
is selected from the group consisting of: (a) hydrocarbyl
substituted succinic anhydrides; (b) hydrolyzed hydrocarbyl
substituted succinic anhydrides; (c) combinations thereof.
7. The method of claim 1 wherein the fuel composition further
comprises: a demulsifier, an antifoam agent, cold flow agent, a
dispersant/detergent additive, or combinations thereof; and wherein
the fuel is susceptible to pick up of oxidative metals to a level
greater than 0.5 ppm when left in contact for an extended period of
time with solid materials containing said metal.
8. The method of claim 7 wherein the dispersant/detergent additive
comprises: succinimide dispersants, quaternary ammonium salts, or
combinations thereof.
9. The method of claim 1 wherein the fuel composition comprises
diesel fuel, biodiesel or combinations thereof.
10. The method of claim 1 wherein the fuel composition is a fuel
additive composition.
11. The method of claim 1 wherein the method also results in the
reduction of injector deposits in an engine in which the fuel
composition of the method is applied.
12. A fuel composition comprising: (a) a fuel; (b) an additive
comprising a hydrocarbon substituted with at least two carboxy
functionalities in the form of acids or at least one carboxy
functionality in the form an anhydride; and (c) optional additional
performance additives.
13. A fuel additive composition comprising: (a) an optional
solvent; (b) an additive comprising a hydrocarbon substituted with
at least two carboxy functionalities in the form of acids or at
least one carboxy functionality in the form an anhydride; and (c)
optional additional performance additives.
14. (canceled)
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to fuel additives, fuel
additive compositions and fuel compositions as well as a method for
fueling an internal combustion engine, providing reduced oxidative
metal pick-up in fuels.
[0002] In the past there has been some uncertainty regarding the
impact of pick-up, or solubilization, of certain oxidative metals
by fuel on engine performance. Such matters have generally been
evaluated from a corrosion control standpoint. However, there is
growing evidence that metal pick-up, for example zinc pick-up, is
an issue that can impact engine performance.
[0003] Trace levels of dissolved or soluble metals, such as zinc
(Zn) and copper (Cu), in fuels, such as diesel fuel, have been
shown to increase injector fouling. Trace metals like these can
enter the fuel distribution system through contamination, or
through the pick-up (dissolution) of metal, by the fuel, from
metals parts that make up part of the fuel distribution system with
which the fuel comes into contact. For example, diesel fuel may
pick up zinc from galvanized steel surfaces in fuel tanks,
resulting in elevated zinc levels in fuels, which may lead to the
accelerated injector fouling, discussed above. Zinc, and other
metals, may also be picked up by the fuel by contacting such
metal-containing surfaces in the vehicle fuel injection system.
[0004] There is a need for fuel additives and fuel compositions
that effectively reduce the amount of metal pick-up, and more
specifically, zinc pick-up while minimizing the impact on additive
and fuel composition costs and complexity.
SUMMARY OF THE INVENTION
[0005] Fuel additives, fuel additive compositions and fuel
compositions have been discovered which reduce the amount of metal
pick-up seen in fuel compositions. The present invention provides
for such compositions as well as a method of reducing contaminant
metal pick-up, such as zinc pick-up, in fuel compositions.
[0006] In accordance with the present invention it has been
discovered that adding an additive, comprising a hydrocarbon
substituted with at least two carboxy functionalities in the form
of acids or at least one carboxy functionality in the form an
anhydride, to a fuel composition results in the reduction of the
amount of oxidative metals pick-up in the fuel composition.
[0007] In some embodiments the substituted hydrocarbon additive is
a hydrocarbyl substituted acylating agent with at least two carboxy
functionalities in the form of acids or anhydrides.
[0008] In some embodiments, the substituted hydrocarbon additive
and/or hydrocarbyl substituted acylating agent has di-acid
functionality. In other embodiments the additive is a succinic
acylating agent. In still other embodiments, which may be used in
combination with one or more of the embodiments described herein,
the hydrocarbyl group of the additive is derived from
polyisobutylene.
[0009] The metal, for which pick-up is being reduced, include group
IV transition metals. In some embodiments, the metal is V, Cr, Mn,
Fe, Co, Ni, Cu, Zn, or combinations thereof. In some embodiments,
the metal may be selected from the group consisting of copper,
zinc, iron, or combinations thereof. In some embodiments, the
oxidative metal is zinc. In other embodiments, the oxidative metal,
for which the tendency of fuel composition to pick up is being
reduced, may be any of the metals, or groups of metals, described
above except iron.
[0010] The present invention also provides for the described method
wherein the substituted hydrocarbon additive may be: (a) a
hydrocarbyl substituted succinic anhydride; (b) a hydrolyzed
hydrocarbyl substituted succinic anhydride; or (c) combinations
thereof.
[0011] In some embodiments the fuel being treated in the method is
susceptible to pick up of oxidative metals to a level greater than
0.5 ppm when left in contact for an extended period of time with
solid materials containing said metal.
[0012] The method of the present invention may also result in the
reduction of injector deposits in an engine in which the fuel
composition of the method is applied.
[0013] The present invention also provides a fuel composition
comprising: (a) a fuel; (b) an additive comprising the substituted
hydrocarbon additive describe herein; and (c) optional additional
performance additives. The present invention also provides a fuel
additive composition comprising: (a) an optional solvent; (b) the
substituted hydrocarbon additive described herein; and (c) optional
additional performance additives.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
Field of the Invention
[0015] The present invention involves a fuel additive, a fuel
additive composition, a fuel composition and a method for fueling
an internal combustion engine. The invention provides a method of
reducing metal-pick, and in some embodiments zinc pick-up, in a
fuel composition, in some embodiment during the operation of an
internal combustion engine.
[0016] The composition of the present invention may be used in fuel
compositions to reduce their tendency to pick-up metals from
surfaces with which they come into contact. The additive
compositions of the present invention may also provide comparable
and/or improved detergency, specifically improved engine deposit
control when they are used in fuel compositions. These
characteristics allow for improved engine performance, including
but not limited to reductions in injector fouling, reduced
deposit-caused engine power losses, reduced deposit-caused fuel
economy losses and reduced deposit-caused engine emissions.
The Substituted Hydrocarbon Additive
[0017] The substituted hydrocarbon additive of the present
invention comprises a hydrocarbon substituted with at least two
carboxy functionalities in the form of acids or at least one
carboxy functionality in the form an anhydride. In some embodiments
the additive is a hydrocarbon substituted with at least two carboxy
functionalities in the form of acids or anhydrides. In other
embodiments the additive is a hydrocarbyl-substituted succinic
acylating agent. In other embodiments the substituted hydrocarbon
additive is a dimer acid compound. In still other embodiments the
substituted hydrocarbon additive of the present invention includes
a combination of two or more of the additives described in this
section.
[0018] The substituted hydrocarbon additives of the present
invention, when used in the compositions and method described
herein, reduce the tendency of fuel compositions in which they are
used to pick up metals.
[0019] The substituted hydrocarbon additives include dimer acids.
Dimer acids are a type of di-acid polymer derived from fatty acids
and/or polyolefins, including the polyalkenes described herein,
which contain acid functionality. IN some embodiments, the dimer
acid used in the present invention is derived from C10 to C20
polyolefins, C12 to C18 polyolefins, and/or C16 to C18
polyolfines.
[0020] The substituted hydrocarbon additives include succinic
acids, halides, anhydrides and combination thereof. In some
embodiments the agents are acids or anhydrides, and in other
embodiments the agents are anhydrides, and in still other
embodiments the agents are hydrolyzed anhydrides. The hydrocarbon
of the substituted hydrocarbon additive and/or the primary
hydrocarbyl group of the hydrocarbyl-substituted succinic acylating
agent generally contains an average of at least about 8, or about
30, or about 35 up to about 350, or to about 200, or to about 100
carbon atoms. In one embodiment, the hydrocarbyl group is derived
from a polyalkene.
[0021] The polyalkene may be characterized by a Mn (number average
molecular weight) of at least about 300. Generally, the polyalkene
is characterized by an Mn of about 500, or about 700, or about 800,
or even about 900 up to about 5000, or to about 2500, or to about
2000, or even to about 1500. In another embodiment n varies between
about 300, or about 500, or about 700 up to about 1200 or to about
1300.
[0022] The polyalkenes include homopolymers and interpolymers of
polymerizable olefin monomers of 2 to about 16 or to about 6, or to
about 4 carbon atoms. The olefins may be monoolefins such as
ethylene, propylene, 1-butene, isobutene, and 1-octene; or a
polyolefinic monomer, such as diolefinic monomer, such
1,3-butadiene and isoprene. In one embodiment, the interpolymer is
a homopolymer. An example of a polymer is a polybutene. In one
instance about 50% of the polybutene is derived from isobutylene.
The polyalkenes are prepared by conventional procedures.
[0023] In one embodiment, the hydrocarbyl groups are derived from
polyalkenes having an n of at least about 1300, or about 1500, or
about 1600 up to about 5000, or to about 3000, or to about 2500, or
to about 2000, or to about 1800, and the Mw/Mn is from about 1.5 or
about 1.8, or about 2, or to about 2.5 to about 3.6, or to about
3.2. In some embodiments the polyalkene is polyisobutylene with a
molecular weight of 800 to 1200. The preparation and use of
substituted hydrocarbons and/or substituted succinic acylating
agents, wherein the hydrocarbon and/or substituent is derived from
such polyalkenes are described in U.S. Pat. No. 4,234,435, the
disclosure of which is hereby incorporated by reference.
[0024] In another embodiment, the substituted hydrocarbon and/or
succinic acylating agents are prepared by reacting the above
described polyalkene with an excess of maleic anhydride to provide
substituted succinic acylating agents wherein the number of
succinic groups for each equivalent weight of substituent group is
at least 1.3, or to about 1.5, or to about 1.7, or to about 1.8.
The maximum number generally will not exceed 4.5, or to about 2.5,
or to about 2.1, or to about 2.0. The polyalkene here may be any of
those described above.
[0025] In another embodiment, the hydrocarbon and/or hydrocarbyl
group contains an average from about 8, or about 10, or about 12 up
to about 40, or to about 30, or to about 24, or to about 20 carbon
atoms. In one embodiment, the hydrocarbyl group contains an average
from about 16 to about 18 carbon atoms. In another embodiment, the
hydrocarbyl group is tetrapropenyl group. In one embodiment, the
hydrocarbyl group is an alkenyl group.
[0026] The hydrocarbon and/or hydrocarbyl group may be derived from
one or more olefins having from about 2 to about 40 carbon atoms or
oligomers thereof. These olefins are preferably alpha-olefins
(sometimes referred to as mono-1-olefins) or isomerized
alpha-olefins. Examples of the alpha-olefins include ethylene,
propylene, butylene, 1-octene, 1-nonene, 1-decene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,
1-henicosene, 1-docosene, 1-tetracosene, etc. Commercially
available alpha-olefin fractions that may be used include the
C.sub.15-18 alpha-olefins, C.sub.12-16 alpha-olefins, C.sub.14-16
alpha-olefins, C.sub.14-18 alpha-olefins, C.sub.16-18
alpha-olefins, C.sub.16-20 alpha-olefins, C.sub.22-28
alpha-olefins, etc. In one embodiment, the olefins are C.sub.16 and
C.sub.16-18 alpha-olefins. Additionally, C.sub.30+ alpha-olefin
fractions such as those available from Gulf Oil Company under the
name Gulftene can be used. In one embodiment, the olefin monomers
include ethylene, propylene and 1-butene.
[0027] Isomerized alpha-olefins are alpha-olefins that have been
converted to internal olefins. The isomerized alpha-olefins
suitable for use herein are usually in the form of mixtures of
internal olefins with some alpha-olefins present. The procedures
for isomerizing alpha-olefins are well known to those in the art.
Briefly these procedures involve contacting alpha-olefin with a
cation exchange resin at a temperature in a range of about
80.degree. to about 130.degree. C. until the desired degree of
isomerization is achieved. These procedures are described for
example in U.S. Pat. No. 4,108,889 which is incorporated herein by
reference.
[0028] The mono-olefins may be derived from the cracking of
paraffin wax. The wax cracking process yields both even and odd
number C.sub.6-20 liquid olefins of which 85% to 90% are straight
chain 1-olefins. The balance of the cracked wax olefins is made up
of internal olefins, branched olefins, diolefins, aromatics and
impurities. Distillation of the C.sub.6-20 liquid olefins, obtained
from the wax cracking process, yields fractions (e.g., C.sub.15-18
alpha-olefins) which are useful in preparing the succinic acylating
agents.
[0029] Other mono-olefins can be derived from the ethylene chain
growth process. This process yields even numbered straight-chain
1-olefins from a controlled Ziegler polymerization. Other methods
for preparing the mono-olefins include
chlorination-dehydrochlorination of paraffin and catalytic
dehydrogenation of paraffins.
[0030] The above procedures for the preparation of mono-olefins are
well known to those of ordinary skill in the art and are described
in detail under the heading "Olefins" in the Encyclopedia of
Chemical Technology, Second Edition, Kirk and Othmer, Supplement,
Pages 632,657, Interscience Publishers, Div. of John Wiley and Son,
1971, which is hereby incorporated by reference for its relevant
disclosures pertaining to methods for preparing mono-olefins.
[0031] Succinic acylating agents are prepared by reacting the
above-described olefins, isomerized olefins or oligomers thereof
with unsaturated carboxylic acylating agents, such as itaconic,
citraconic, or maleic acylating agents at a temperature of about
160.degree., or about 185.degree. C. up to about 240.degree. C., or
to about 210.degree. C. Maleic acylating agents are the preferred
unsaturated acylating agent. The procedures for preparing the
acylating agents are well known to those skilled in the art and
have been described for example in U.S. Pat. No. 3,412,111; and Ben
et al, "The Ene Reaction of Maleic Anhydride With Alkenes", J. C.
S. Perkin II (1977), pages 535-537. These references are
incorporated by reference for their disclosure of procedures for
making the above acylating agents. In one embodiment, the alkenyl
group is derived from oligomers of lower olefins, i.e., olefins
containing from 2 to about 6, or about 4 carbon atoms. Examples of
these olefins include ethylene, propylene and butylene.
[0032] The olefin, olefin oligomer, or polyalkene may be reacted
with the carboxylic reagent such that there is at least one mole of
carboxylic reagent for each mole of olefin, olefin oligomer, or
polyalkene that reacts. Preferably, an excess of carboxylic reagent
is used. In one embodiment, this excess is between about 5% to
about 25%. In another embodiment, the excess is greater than 40%,
or greater than 50%, and even greater than 70%.
[0033] The conditions, i.e., temperature, agitation, solvents, and
the like, for forming the hydrocarbyl-substituted succinic
acylating agent, are known to those in the art. Examples of patents
describing various procedures for preparing useful acylating agents
include U.S. Pat. Nos. 3,172,892 (Le Suer et al.); 3,215,707
(Rense); 3,219,666 (Norman et al); 3,231,587 (Rense); 3,912,764
(Palmer); 4,110,349 (Cohen); and 4,234,435 (Meinhardt et al); and
U.K. 1,440,219. The disclosures of these patents are hereby
incorporated by reference.
[0034] In some embodiments the substituted hydrocarbon additives
and/or hydrocarbyl substituted succinic acylating agents suitable
for use in the present invention contain di-acid functionality. In
other embodiments, which may be used alone or in combination with
the embodiments described above, the hydrocarbyl group of the
hydrocarbyl substituted succinic acylating agent is derived from
polyisobutylene and the di-acid functionality of the agent is
derived from carboxylic acid groups, such as hydrocarbyl
substituted succinic acid.
[0035] In some embodiments the hydrocarbyl substituted acylating
agent comprises one or more hydrocarbyl substituted succinic
anhydride groups. In some embodiments the hydrocarbyl substituted
acylating agent comprises one or more hydrolyzed hydrocarbyl
substituted succinic anhydride groups.
[0036] In some embodiments the hydrocarbyl substituents of the
acylating agents described above are derived from homopolymers
and/or copolymers containing 2 to 10 carbon atoms. In some
embodiments the hydrocarbyl substituents of any of the acylating
agents described above are derived from polyisobutylene.
[0037] The fuel additives of the present invention can be solids,
semi-solids, or liquids (oils) depending on the particular
alcohol(s) and/or amine(s) used in preparing them. For use as
additives in oleaginous compositions including lubricating and fuel
compositions the fuel additives are advantageously soluble and/or
stably dispersible in such oleaginous compositions. Thus, for
example, compositions intended for use in fuels are typically
fuel-soluble and/or stably dispersible in a fuel in which they are
to be used. The term "fuel-soluble" as used in this specification
and appended claims does not necessarily mean that all the
compositions in question are miscible or soluble in all proportions
in all fuels. Rather, it is intended to mean that the composition
is soluble in a fuel (hydrocarbon, non-hydrocarbon, mixtures, etc)
in which it is intended to function to an extent which permits the
solution to exhibit one or more of the desired properties.
Similarly, it is not necessary that such "solutions" be true
solutions in the strict physical or chemical sense. They may
instead be micro-emulsions or colloidal dispersions which, for the
purpose of this invention, exhibit properties sufficiently close to
those of true solutions to be, for practical purposes,
interchangeable with them within the context of this invention.
[0038] As previously indicated, the anti-metal pick-up additives of
this invention are useful as additives for fuels, in which they may
also function as detergents. The fuel additives of the present
invention can be present in fuel compositions at 1 to 10,000 ppm
(where ppm is calculated on a weight:weight basis). In additional
embodiments, the fuel additive is present in fuel compositions in
ranges with lower limits of 1, 3, 5, 10, 50, 100, 150 and 200 ppm
and upper limits of 10,000, 7,500, 5,000, and 2,500 where any upper
limit may be combined with any lower limit to provide a range for
the fuel additive present in the fuel compositions.
[0039] It is contemplated that the additives of the present
invention may form salts or other complexes and/or derivatives,
when interacting with other components of the compositions in which
they are used. Such forms of these additives are also part of the
present invention and are include in the embodiment described
herein. Some of the succinic acylating agents of the present
invention and the processes for making them are disclosed in U.S.
Pat. Nos. 5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500;
and 6,114,547 which are hereby incorporated by reference. Other
methods of making the hydrocarbyl substituted acylating agent can
be found in U.S. Pat. Nos. 5,912,213; 5,851,966; and 5,885,944
which are hereby incorporated by reference. In some embodiments the
succinic acylating agents of the present invention are prepared by
the thermal process and/or chlorine free process only, as described
in EP0355895 hereby incorporated by reference.
The Fuel Additive Compositions
[0040] The fuel additive composition of the present invention
comprises the fuel additive described above and further comprises a
solvent and/or one or more additional performance additives. These
additive compositions, also known as additive concentrates and/or
concentrates, may be used to prepare fuel compositions by adding
the additive composition to an non-additized fuel.
[0041] The solvents suitable for use in the present invention
include hydrocarbon solvents that provide for the additive
composition's compatibility and/or homogeneity and to facilitate
their handling and transfer and may include a fuel as described
below. The solvent can be an aliphatic hydrocarbon, an aromatic
hydrocarbon, an oxygen-containing composition, or a mixture
thereof. In some embodiments the flash point of the solvent is
generally about 25.degree. C. or higher. In some embodiments the
hydrocarbon solvent is an aromatic naphtha having a flash point
above 62.degree. C. or an aromatic naphtha having a flash point of
40.degree. C. or a kerosene with a 16% aromatic content having a
flash point above 62.degree. C.
[0042] Aliphatic hydrocarbons include various naphtha and kerosene
boiling point fractions that have a majority of aliphatic
components. Aromatic hydrocarbons include benzene, toluene, xylenes
and various naphtha and kerosene boiling point fractions that have
a majority of aromatic components. Alcohols are usually aliphatic
alcohols having about 2 to 10 carbon atoms and include ethanol,
1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, amyl
alcohol, and 2-methyl-1-butanol.
[0043] The oxygen containing composition can include an alcohol, a
ketone, an ester of a carboxylic acid, a glycol and/or a
polyglycol, or a mixture thereof. The solvent in an embodiment of
the invention will be substantially free of to free of sulphur
having a sulphur content in several instances that is below 50 ppm,
25 ppm, below 18 ppm, below 10 ppm, below 8 ppm, below 4 ppm, or
below 2 ppm. The solvent can be present in the additive concentrate
composition at 0 to 99 percent by weight, and in other instances at
3 to 80 percent by weight, or 10 to 70 percent by weight. The
friction modifier of the present invention and the additional
performance additives taken separately or in combination can be
present in the additive concentrate composition at 0.01 to 100
percent by weight, and in other instances can be present at 0.01 to
95 percent by weight, at 0.01 to 90 percent by weight, or at 0.1 to
80 percent by weight.
[0044] As allowed for by the ranges above, in one embodiment, the
additive concentrate may comprise the fuel additive of the present
invention and be substantially free of any additional solvent. In
these embodiments the additive concentrate containing the fuel
additive of the present invention is neat, in that it does not
contain any additional solvent added to improve the material
handling characteristics of the concentrate, such as its
viscosity.
[0045] In several embodiments of the invention the fuel
composition, fuel additive concentrate, and/or the fuel additive
itself are substantially free of or free of at least one member
selected from the group consisting of sulphur, phosphorus, sulfated
ash, and combinations thereof, and in other embodiments the fuel
composition contains less than 50 ppm, 20 ppm, less than 15 ppm,
less than 10 ppm, or less than 1 ppm of any one or all of these
members.
[0046] In an embodiment of the invention the additive concentrate
composition, or a fuel composition containing the fuel additive of
the present invention, may be prepared by admixing or mixing the
components of the composition at ambient to elevated temperatures
usually up to 60.degree. C. until the composition is
homogeneous.
[0047] The additional performance additives which may be included
in the additive compositions of the present invention are described
below.
The Fuel
[0048] The fuel composition of the present invention comprises the
fuel additive described above and a liquid fuel, and is useful in
fueling an internal combustion engine. A fuel may also be a
component of the additive compositions described above.
[0049] It is generally accepted in the industry that many types of
commercial fuel, particularly market diesel fuels and/or biofuels,
have the capacity to pick up, or solubilize, some level of
oxidative metal when placed in direct contact with susceptible
metal surfaces. There is also evidence that most if not all fuels,
particularly market diesel fuels have some tendency to pick up
metals. It has also been recognized that many fuel additives may
increase the tendency of the fuel to pick up oxidative metals in
the fuel and fuel additive compositions in which they are used. The
present invention reduces the propensity to pick up oxidative
metals in such fuel and fuel additive compositions.
[0050] In some embodiments, the fuels suitable for use in the
present invention include any commercially available fuels, and in
some embodiments any commercially available diesel fuels and/or
biofuels. In other embodiments, the fuels suitable for use in the
present invention include any commercially available fuels which
are susceptible to metal pick up, and in some embodiments any
commercially available diesel fuels and/or biofuels susceptible to
metal pick up.
[0051] In still other embodiments, the fuels suitable for use in
the present invention are any fuels, or any diesel fuels and/or
biofuels, which are susceptible to pick up of oxidative metals to a
level greater than 0.5 ppm when left in contact for an extended
period of time with solid materials containing said metal. In some
embodiments the exposure time involved is greater than 72 hours,
greater than 48 hours, or greater than 24 hours.
[0052] The present invention includes fuel compositions and fuel
additive concentrate compositions which may contain fuel. The fuel
used in these compositions may or may not exhibit a propensity to
pick up oxidative metal, and may in fact be any of the fuels
described in this application or combinations thereof. The fuel
used in these compositions need not be the same fuel to which the
additive of the present invention may be added in the methods
described herein. That is, the additive of the present invention
may be present in a composition that also comprises a fuel. This
fuel may or may not exhibit a propensity to pick up oxidative
metal. The additive-containing composition may then be added to a
fuel and/or fuel additive composition. The identity of the fuel
present in this composition is independent of the identity of the
optional fuel component in the additive containing composition. The
oxidative metal pick-up propensity of the fuel and/or fuel additive
composition may be a result of the properties of the fuel and/or
the properties of one or more of the additives present in the fuel
and/or additive composition. The addition of the
additive-containing compositions, as described in the method and
compositions of the present invention result in a reduction of the
oxidative metal pick-up propensity of the fuel and/or fuel additive
compositions.
[0053] The description that follows of the types of fuels suitable
for use in the present invention refer to the fuel that may be
present in the additive containing compositions of the present
invention as well as the fuel and/or fuel additive compositions to
which the additive containing compositions may be added.
[0054] Fuels suitable for use in the present invention are not
overly limited. Generally, suitable fuels are normally liquid at
ambient conditions e.g., room temperature (20 to 30.degree. C.).
The liquid fuel can be a hydrocarbon fuel, a non-hydrocarbon fuel,
or a mixture thereof.
[0055] The hydrocarbon fuel can be a petroleum distillate,
including a gasoline as defined by ASTM specification D4814, or a
diesel fuel, as defined by ASTM specification D975. In one
embodiment the liquid fuel is a gasoline, and in another embodiment
the liquid fuel is a non-leaded gasoline. In another embodiment the
liquid fuel is a diesel fuel. The hydrocarbon fuel can be a
hydrocarbon prepared by a gas to liquid process to include for
example hydrocarbons prepared by a process such as the
Fischer-Tropsch process. In some embodiments, the fuel used in the
present invention is a diesel fuel, a biodiesel fuel, or
combinations thereof.
[0056] The non-hydrocarbon fuel can be an oxygen containing
composition, often referred to as an oxygenate, which includes an
alcohol, an ether, a ketone, an ester of a carboxylic acid, a
nitroalkane, or a mixture thereof. The non-hydrocarbon fuel can
include for example methanol, ethanol, methyl t-butyl ether, methyl
ethyl ketone, transesterified oils and/or fats from plants and
animals such as rapeseed methyl ester and soybean methyl ester, and
nitromethane.
[0057] Mixtures of hydrocarbon and non-hydrocarbon fuels can
include, for example, gasoline and methanol and/or ethanol, diesel
fuel and ethanol, and diesel fuel and a transesterified plant oil
such as rapeseed methyl ester and other bio-derived fuels. In one
embodiment the liquid fuel is an emulsion of water in a hydrocarbon
fuel, a non-hydrocarbon fuel, or a mixture thereof. In several
embodiments of this invention the liquid fuel can have a sulphur
content on a weight basis that is 5000 ppm or less, 1000 ppm or
less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm
or less.
[0058] The liquid fuel of the invention is present in a fuel
composition in a major amount that is generally greater than 95% by
weight, and in other embodiments is present at greater than 97% by
weight, greater than 99.5% by weight, or greater than 99.9% by
weight.
Additional Performance Additives
[0059] The additive compositions and fuel compositions of the
present invention can further comprise one or more additional
performance additives. Additional performance additives can be
added to a fuel composition depending on several factors to include
the type of internal combustion engine and the type of fuel being
used in that engine, the quality of the fuel, and the service
conditions under which the engine is being operated.
[0060] In some embodiments, the additional performance additives
described herein may increase the tendency of a fuel composition to
pick-up metals such as zinc. The use of the present invention in
such situations can reduce and/or eliminate this impact of the
additional additives.
[0061] The additional performance additives can include: an
antioxidant such as a hindered phenol or derivative thereof and/or
a diarylamine or derivative thereof; a corrosion inhibitor; and/or
a detergent/dispersant additive, other than the fuel additive of
the present invention, such as a polyetheramine or nitrogen
containing detergent, including but not limited to PIB amine
dispersants, quaternary salt dispersants, and succinimide
dispersants including derivates of succinimide dispersants such as
quaternary ammonium salts thereof.
[0062] The additional performance additives may also include: a
cold flow improver such as an esterified copolymer of maleic
anhydride and styrene and/or a copolymer of ethylene and vinyl
acetate; a foam inhibitor and/or antifoam agent such as a silicone
fluid; a demulsifier such as a polyalkoxylated alcohol; a lubricity
agent such as a fatty carboxylic acid; a metal deactivator such as
an aromatic triazole or derivative thereof, including but not
limited to benzotriazole; and/or a valve seat recession additive
such as an alkali metal sulfosuccinate salt.
[0063] Suitable antifoams also include organic silicones such as
polydimethyl siloxane, polyethylsiloxane, polydiethylsiloxane,
polyacrylates and polymethacrylates,
trimethyl-trifluoro-propylmethyl siloxane and the like.
[0064] The additional additives may also include a biocide; an
antistatic agent, a deicer, a fluidizer such as a mineral oil
and/or a poly(alpha-olefin) and/or a polyether, and a combustion
improver such as an octane or cetane improver.
[0065] The additional performance additives, which may be present
in the fuel additive compositions and fuel compositions of the
present invention, also include di-ester, di-amide, ester-amide,
and ester-imide friction modifiers prepared by reacting a
dicarboxylic acid (such as tartaric acid) and/or a tricarboxylic
acid (such as citric acid), with an amine and/or alcohol,
optionally in the presence of a known esterification catalyst.
These friction modifiers, often derived from tartaric acid, citric
acid, or derivatives thereof, may be derived from amines and/or
alcohols that are branched so that the friction modifier itself has
significant amounts of branched hydrocarbyl groups present within
it structure. Examples of a suitable branched alcohols used to
prepare these friction modifiers include 2-ethylhexanol,
isotridecanol, Guerbet alcohols, or mixtures thereof.
[0066] The additional performance additives may comprise a high TBN
nitrogen containing dispersant, such as a succinimide dispersant,
that is the condensation product of a hydrocarbyl-substituted
succinic anhydride with a poly(alkyleneamine). Succnimide
dispersants are very well known in the art of lubricant
formulation. Such molecules are commonly derived from reaction of
an alkenyl acylating agent with a polyamine, and a wide variety of
linkages between the two moieties is possible including a simple
imide structure as well as a variety of amides and quaternary
ammonium salts. Succinimide dispersants are more fully described in
U.S. Pat. Nos. 4,234,435 and 3,172,892. Such materials may also
contain ester linkages or ester functionality.
[0067] Another class of nitrogen-containing dispersant is the
Mannich bases. These are materials which are formed by the
condensation of a higher molecular weight, alkyl substituted
phenol, an alkylene polyamine, and an aldehyde such as
formaldehyde. Such materials are described in more detail in U.S.
Pat. No. 3,634,515.
[0068] Other nitrogen-containing dispersants include polymeric
dispersant additives, which are generally hydrocarbon-based
polymers which contain nitrogen-containing polar functionality to
impart dispersancy characteristics to the polymer.
[0069] An amine is typically employed in preparing the high TBN
nitrogen-containing dispersant. One or more poly(alkyleneamine)s
may be used, and these may comprise one or more
poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6
nitrogens. Such materials include triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
Such materials are typically commercially available as mixtures of
various isomers containing a range number of ethylene units and
nitrogen atoms, as well as a variety of isomeric structures,
including various cyclic structures. The poly(alkyleneamine) may
likewise comprise relatively higher molecular weight amines known
in the industry as ethylene amine still bottoms.
[0070] The additional performance additives may comprise a
quaternary salt comprising the reaction product of: (i) at least
one compound selected from the group consisting of: (a) the
condensation product of a hydrocarbyl-substituted acylating agent
and a compound having an oxygen or nitrogen atom capable of
condensing with said acylating agent and said condensation product
further having a tertiary amino group; (b) a polyalkene-substituted
amine having at least one tertiary amino group; and (c) a Mannich
reaction product having a tertiary amino group, said Mannich
reaction product being prepared from the reaction of a
hydrocarbyl-substituted phenol, an aldehyde, and an amine; and (ii)
a quaternizing agent suitable for converting the tertiary amino
group of compound (i) to a quaternary nitrogen, wherein the
quaternizing agent is selected from the group consisting of dialkyl
sulfates, benzyl halides, hydrocarbyl substituted carbonates;
hydrocarbyl epoxides in combination with an acid or mixtures
thereof.
[0071] In one embodiment the quaternary salt comprises the reaction
product of (i) at least one compound selected from the group
consisting of: a polyalkene-substituted amine having at least one
tertiary amino group and/or a Mannich reaction product having a
tertiary amino group; and (ii) a quaternizing agent.
[0072] In another embodiment the quaternary salt comprises the
reaction product of (i) the reaction product of a succinic
anhydride and an amine; and (ii) a quaternizing agent. In such
embodiments, the succinic anhydride may be derived from
polyisobutylene and an anhydride, where the polyisobutylene has a
number average molecular weight of about 800 to about 1600. In some
embodiments the succinic anhydride is chlorine free.
[0073] In some embodiments, the hydrocarbyl substituted acylating
agent of component (i)(a) described above is the reaction product
of a long chain hydrocarbon, generally a polyolefin substituted
with a monounsaturated carboxylic acid reactant such as (1)
monounsaturated C.sub.4 to C.sub.10 dicarboxylic acid such as
fumaric acid, itaconic acid, maleic acid.; (2) derivatives of (1)
such as anhydrides or C.sub.1 to C.sub.5 alcohol derived mono- or
di-esters of (1); (3) monounsaturated C.sub.3 to C.sub.10
monocarboxylic acid such as acrylic acid and methacrylic acid.; or
(iv4 derivatives of (3) such as C.sub.1 to C.sub.5 alcohol derived
esters of (3) with any compound containing an olefinic bond
represented by the general formula:
(R.sup.1)(R.sup.1)C.dbd.C(R.sup.1)(CH(R.sup.1)(R.sup.1)) (I)
wherein each R.sup.1 is independently hydrogen or a hydrocarbyl
group.
[0074] Olefin polymers for reaction with the monounsaturated
carboxylic acids can include polymers comprising a major molar
amount of C.sub.2 to C.sub.20, e.g. C.sub.2 to C.sub.5 monoolefin.
Such olefins include ethylene, propylene, butylene, isobutylene,
pentene, octene-1, or styrene. The polymers can be homopolymers
such as polyisobutylene, as well as copolymers of two or more of
such olefins such as copolymers of; ethylene and propylene;
butylene and isobutylene; propylene and isobutylene. Other
copolymers include those in which a minor molar amount of the
copolymer monomers e.g., 1 to 10 mole % is a C.sub.4 to C.sub.18
diolefin, e.g., a copolymer of isobutylene and butadiene; or a
copolymer of ethylene, propylene and 1,4-hexadiene.
[0075] In one embodiment, at least one R of formula (I) is derived
from polybutene, that is, polymers of C.sub.4 olefins, including
1-butene, 2-butene and isobutylene. C.sub.4 polymers can include
polyisobutylene. In another embodiment, at least one R of formula
(I) is derived from ethylene-alpha olefin polymers, including
ethylene-propylene-diene polymers. Ethylene-alpha olefin copolymers
and ethylene-lower olefin-diene terpolymers are described in
numerous patent documents, including European patent publication
EP0279863 and the following U.S. Pat. Nos. 3,598,738; 4,026,809;
4,032,700; 4,137,185; 4,156,061; 4,320,019; 4,357,250; 4,658,078;
4,668,834; 4,937,299; 5,324,800 each of which are incorporated
herein by reference for relevant disclosures of these ethylene
based polymers.
[0076] In another embodiment, the olefinic bonds of formula (I) are
predominantly vinylidene groups, represented by the following
formulas:
--(H)C.dbd.C(R.sup.2)(R.sup.2) (II)
wherein R.sup.2 is a hydrocarbyl group, and in some embodiments
both R.sup.2 groups are methyl groups, and
--(H)(R.sup.3)C(C(CH.sub.3).dbd.CH2) (III)
wherein R.sup.3 is a hydrocarbyl group.
[0077] In one embodiment, the vinylidene content of formula (I) can
comprise at least about 30 mole % vinylidene groups, at least about
50 mole % vinylidene groups, or at least about 70 mole % vinylidene
groups. Such material and methods for preparing them are described
in U.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823,
5,408,018, 6,562,913, 6,683,138, 7,037,999 and U.S. Publication
Nos. 20040176552A1, 20050137363 and 20060079652A1, which are
expressly incorporated herein by reference, such products are
commercially available by BASF, under the tradename GLISSOPAL.RTM.
and by Texas Petrochemicals LP, under the tradename TPC 1105.TM.
and TPC 595.TM..
[0078] Methods of making hydrocarbyl substituted acylating agents
from the reaction of the monounsaturated carboxylic acid reactant
and the compound of formula (I) are well know in the art and
disclosed in the following patents: U.S. Pat. Nos. 3,361,673 and
3,401,118 to cause a thermal "ene" reaction to take place; U.S.
Pat. Nos. 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587;
3,912,764; 4,110,349; 4,234,435; 6,077,909; 6,165,235 and are
hereby incorporated by reference.
[0079] In another embodiment, the hydrocarbyl substituted acylating
agent can be made from the reaction of at least one carboxylic
reactant represented by the following formulas:
##STR00001##
wherein each R.sup.4 is independently H or a hydrocarbyl group, and
each R.sup.5 is a divalent hydrocarbylene group and n is 0 or 1
with any compound containing an olefin bond as represented by
formula (I). Compounds and the processes for making these compounds
are disclosed in U.S. Pat. Nos. 5,739,356; 5,777,142; 5,786,490;
5,856,524; 6,020,500; and 6,114,547 which are hereby incorporated
by reference.
[0080] Other methods of making the hydrocarbyl substituted
acylating agent can be found in the following reference, U.S. Pat.
Nos. 5,912,213; 5,851,966; and 5,885,944 which are hereby
incorporated by reference.
[0081] The compound having an oxygen or nitrogen atom capable of
condensing with the acylating agent and further having a tertiary
amino group can be represented by the following formulas:
##STR00002##
wherein X is a alkylene group containing about 1 to about 4 carbon
atoms; and wherein each R.sup.6 is independently a hydrocarbyl
group, and R.sup.6' can be hydrogen or a hydrocarbyl group.
##STR00003##
wherein X is a alkylene group containing about 1 to about 4 carbon
atoms; and wherein each R.sup.7 is independently a hydrocarbyl
group.
[0082] Examples of the nitrogen or oxygen contain compounds capable
of condensing with the acylating agent and further having a
tertiary amino group can include but are not limited to:
ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, the
isomeric butylenediamines, pentanediamines, hexanediamines,
heptanediamines, diethylenetriamine, dipropylenetriamine,
dibutylenetriamine, triethylenetetraamine, tetraethylenepentaamine,
pentaethylenehexaamine, hexamethylenetetramine, and
bis(hexamethylene) triamine, the diaminobenzenes, the
diaminopyridines or mixtures thereof. In addition, nitrogen or
oxygen contain compounds which may be alkylated to contain a
tertiary amino group may also used. Examples of the nitrogen or
oxygen contain compounds capable of condensing with the acylating
agent after being alkylated to having a tertiary amino group can
include but are not limited to: dimethyl-aminopropylamine,
N,N-dimethyl-aminopropylamine, N,N-diethylaminopropylamine,
N,N-dimethyl-aminoethylamine or mixtures thereof. The nitrogen or
oxygen containing compounds capable of condensing with the
acylating agent and further having a tertiary amino group can
further include aminoalkyl substituted heterocyclic compounds such
as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine,
1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine,
3'3-aminobis(N,N-dimethylpropylamine). Another type of nitrogen or
oxygen containing compounds capable of condensing with the
acylating agent and having a tertiary amino group include
alkanolamines including but not limited to triethanolamine,
N,N-dimethylaminopropanol, N,N-diethylaminopropanol,
N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, or mixtures
thereof.
[0083] Examples of quaternary ammonium salt and methods for
preparing the same are described in the following patents, which
are hereby incorporated by reference, U.S. Pat. No. 4,253,980, U.S.
Pat. No. 3,778,371, U.S. Pat. No. 4,171,959, U.S. Pat. No.
4,326,973, U.S. Pat. No. 4,338,206, and U.S. Pat. No.
5,254,138.
[0084] The additional performance additives can each be added
directly to the additive and/or the fuel compositions of the
present invention, but they are generally mixed with the fuel
additive to form an additive composition, or concentrate, which is
then mixed with fuel to result in a fuel composition. The additive
concentrate compositions are described in more detail above.
[0085] In some embodiments, these additional performance additives
described above may be the cause and/or a contributing factor to
the propensity of a fuel to pick up oxidative metal in the fuel
compositions in which they are used. In other embodiments, the
additives described above may have no impact on the metal pick-up
properties of the fuel composition in which they are used. In
either case, the additive compositions and methods of the present
invention can counter the potential effect of these additives and
reduce the tendency of fuel compositions to pick-up metals, whether
that tendency is caused, exacerbated by, or not significantly
changes by, the additional performance additives described
above.
INDUSTRIAL APPLICATION
[0086] In one embodiment the invention is useful for a liquid fuel
and/or for the operation of an internal combustion engine,
including either compression ignition engines or spark ignited
engines. The internal combustion engine includes 2-stroke or
4-stroke engines fuelled with gasoline, diesel, a natural gas, a
mixed gasoline/alcohol or any of the fuels described in the
sections above. The compression ignition engines include both light
duty and heavy duty diesel engines. The spark ignited engines
include port and direct injection gasoline engines.
[0087] In other embodiments the invention is useful in additive
compositions in that the fuel additive and methods described above
reduce metal pick-up in fuel compositions, thus preventing elevated
levels of metals, such as zinc, in the fuel.
[0088] In still other embodiments the additive compositions of the
present invention may be used in a lubricating composition such
that the additives are present in the lubricating system of the
engine. The additives may also enter the combustion chamber of the
engine during operation of the engine by the transfer of small
amounts of the additive containing lubricating composition to the
combustion chamber due to a phenomenon referred to as "blow by"
where the lubricating composition, and in this case the additive
composition, pass around the piston heads inside the cylinder,
moving from the lubricating system of the engine into the
combustion chamber.
[0089] In some embodiments the methods and/or compositions of the
present invention provide a reduction in metal pick-up of at least
5%, at least 20% or even at least 50%. In some of these embodiments
the reduction is in regards to the 7 day and/or 14 day result of
the test procedure used in the examples below. In other embodiments
the methods and/or compositions of the present invention ensure the
metal level of a fuel composition does not rise above 10 ppm, 5
ppm, 1 ppm. 0.5 ppm, 0.3 ppm or even 0.1 ppm of metal content. In
some of these embodiments the reduction is in regards to the 7 day
and/or 14 day result of the test procedure used in the examples
below. In some embodiments, the methods and/or compositions of the
present invention, when evaluated at 7 days by the test described
in the examples below, provide a reduction in metal levels of at
least 30%, or at least 80% and/or ensure metal levels to not rise
above 1 ppm. In some embodiments, the methods and/or compositions
of the present invention, when evaluated at 14 days by the test
described in the examples below, provide a reduction in metal
levels of at least 40%, or at least 80% and/or ensure metal levels
to not rise above 8 ppm, or even 1 ppm.
[0090] The present invention includes the use of the substituted
hydrocarbon and/or hydrocarbyl substituted acylating agents
described herein as additives in fuel compositions, as well as the
additive itself and the fuel and fuel additive compositions
containing said additive. The additives of the present invention
may be delivered to the fuel compositions and/or fuel additive
compositions in any of the means known in the art and the timing of
the additive is not limited. In other words, the additive of the
present invention may be added to a fuel composition before,
during, or after the production and/or blending of the fuel and/or
additive composition. The additive of the invention may be added to
fuel and/or additive composition before, during, or after the
addition of other performance additives which may be used in the
compositions. The additive of the invention may be added as a top
treat to fuel and/or additive compositions or be incorporated into
the production and/or distribution of the fuel and/or additive
compositions in which it is used.
[0091] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: 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 a ring);
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent (e.g., halo (especially chloro and fluoro), hydroxy,
alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
hetero substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this
invention, contain other than carbon in a ring or chain otherwise
composed of carbon atoms. Heteroatoms include sulfur, oxygen,
nitrogen, and encompass substituents as pyridyl, furyl, thienyl and
imidazolyl. In general, no more than two, preferably no more than
one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0092] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. In addition
the acylating agents and/or substituted hydrocarbon additives of
the present invention may form salts or other complexes and/or
derivatives, when interacting with other components of the
compositions in which they are used. The products formed thereby,
including the products formed upon employing the composition of the
present invention in its intended use, may not be susceptible of
easy description. Nevertheless, all such modifications and reaction
products are included within the scope of the present invention;
the present invention encompasses the composition prepared by
admixing the components described above.
EXAMPLES
[0093] The invention will be further illustrated by the following
examples, which sets forth particularly advantageous embodiments.
While the examples are provided to illustrate the present
invention, they are not intended to limit it.
Example Set 1
[0094] Fuel treated with a succinimide dispersant. An EU
certification diesel fuel, known as RF-06, is treated with 200 ppm
of a commercially available succinimide dispersant. Seven 500 mL
graduated cylinder are prepared for testing by placing in each a 4
cm section of a Goodfellow Zn rod ZN007902, having a length of 200
mm and a diameter of 2.0 mm. The weight of each rod section is
recorded and an amount of fuel is added to each cylinder so that
the combined mixture of fuel composition and zinc rod is 1% by
weight zinc. Each cylinder is charged with a slightly different
amount of fuel to ensure the zinc content of each sample is the
same. One of the seven samples (1-1) is kept as a baseline. The
other seven samples (1-2 to 1-7) are each independently treated at
200 ppm with an additional additive, as shown the in the table
below.
TABLE-US-00001 TABLE 1 Additional Additives Added to Test Samples
Sample Additional Additive (at 200 ppm in the Fuel) 1-1
None-Baseline 1-2 ~1000 MW Hydrolyzed PIBSA-Hydrolyzed
polyisobutylene succinic anhydride wherein the polyisobutylene has
a number average molecular weight of about 1000. 1-3 ~550 MW
PIBSA-Polyisobutylene succinic anhydride wherein the
polyisobutylene has a number average molecular weight of about 550.
1-4 Pentasize 68F-A commercially available succinic anhydride
derived from C16-C18 polyolefin. 1-5 Dimer Acid (hydrogenated)-A
commercially available acid product containing two carboxyl groups,
purchased from Aldrich under catalog ID 432369-1L. 1-6 ~1000 MW
PIBSA-Polyisobutylene succinic anhydride wherein the
polyisobutylene has a number average molecular weight of about
1000, which is not hydrolyzed 1-7 ~1000 MW Mono Esterified
PIBSA-Esterified polyiso- butylene succinic anhydride wherein the
polyisobutylene has a number average molecular weight of about
1000, which is not hydrolyzed, and which is esterified with 1 equiv
of n-butanol.
[0095] The containers are stored at ambient conditions in a dark
test location for 14 days. Each sample is tested at the 7 day mark
and the 14 day mark by Inductively Coupled Plasma (ICP) analysis to
determine zinc content. The results of Example Set 1 are summarized
in the table below.
TABLE-US-00002 TABLE 2 Results from Example Set 1. Additional
Additive Zinc Level (ppm) Zinc Level (ppm) Sample (at 200 ppm in
the Fuel) at 7 Days at 14 Days 1-1 None-Baseline 0.6 1.3 1-2 ~1000
MW Hydrolyzed 0.1 0.1 PIBSA 1-3 ~550 MW PIBSA 0.1 0.1 1-4 Pentasize
68F 0.0 0.1 1-5 Dimer Acid (hydrogenated) 1-6 ~1000 mw PIBSA 0.1
0.1 1-7 ~1000 MW Mono 0.4 0.8 Esterified PIBSA
Example Set 2
[0096] Biodiesel. Example set 1 is repeated except that the
succinimide dispersant treated diesel fuel is replaced with B100, a
commercially available biodiesel fuel. In addition, each additional
additive in samples 2-2 to 2-7 are present in the fuel composition
at 500 ppm. Samples 2-1 to 2-7 are tested in the same manner
described above and the results are summarized in the table
below.
TABLE-US-00003 TABLE 3 Results from Example Set 2. Additional
Additive Zinc Level (ppm) Zinc Level (ppm) Sample (at 500 ppm in
the B100) at 7 Days at 14 Days 2-1 None-Baseline 1.5 1.7 2-2 ~1000
MW Hydrolyzed 0.2 0.3 PIBSA 2-3 ~500 MW PIBSA 0.3 0.3 2-4 Pentasize
68F 0.2 0.2 2-5 Dimer Acid 0.5 0.8 (hydrogenated) 2-6 ~1000 MW
PIBSA 2-7 ~1000 MW Mono 3.0 3.8 Esterified PIBSA
[0097] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicates all
percent values and ppm values herein are weight percent values
and/or calculated on a weight basis. Unless otherwise indicated,
each chemical or composition referred to herein should be
interpreted as being a commercial grade material which may contain
the isomers, by-products, derivatives, and other such materials
which are normally understood to be present in the commercial
grade. However, the amount of each chemical component is presented
exclusive of any solvent or diluent, which may be customarily
present in the commercial material, unless otherwise indicated. It
is to be understood that the upper and lower amount, range, and
ratio limits set forth herein may be independently combined.
Similarly, the ranges and amounts for each element of the invention
can be used together with ranges or amounts for any of the other
elements. As used herein, the expression "consisting essentially
of" permits the inclusion of substances that do not materially
affect the basic and novel characteristics of the composition under
consideration.
[0098] In addition, all the embodiments described above have been
contemplated as to their use, both alone and in combination, with
all of the other embodiments described above, and these
combinations are considered to be part of the present invention.
The specific embodiments of amines and alcohols described above
have been contemplated in combination with the specific embodiments
of the carboxylic acids useful in the present invention.
* * * * *