Note: Descriptions are shown in the official language in which they were submitted.
TITLE
ADDITIVES TO REDUCE METAL PICK-UP IN FUELS
This application is a divisional of Canadian Patent Application No. 2,739,432
filed October 1, 2009.
BACKGROUND OF THE INVENTION
[0001] The present invention relates to fuel additives, fuel additive
composi-
tions and fuel compositions as well as a method for fueling an internal combus-
tion 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 per-
formance. 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 met-
als, 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
effec-
tively reduce the amount of metal pick-up, and more specifically, zinc pick-up
while minimizing the impact on additive and fuel composition costs and com-
plexity.
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 compo-
sitions. The present invention provides for such compositions as well as a
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CA 3025740 2018-11-29
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 function alities 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 embodi-
ments, which may be used in combination with one or more of the embodiments
described herein, the hydrocarbyl group of the additive is derived from
polyiso-
butylene.
[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 anhy-
dride; or (c) combinations thereof.
[00111 In some embodiments the fuel being treated in the method is
suscep-
tible 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.
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[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
compo-
sition, 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
compo-
sitions 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 de-
posit-caused fuel economy losses and reduced deposit-caused engine emissions.
The Substituted Hydrocarbon Additive
[0017] The substituted hydrocarbon additive of the present invention
com-
prises 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 functionalitics in the form of acids or anhydrides. In other embodi-
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CA 3025740 2018-11-29
ments the additive is a hydrocarbyl-substituted succinic acylating agent. In
other embodiments the substituted hydrocarbon additive is a dimer acid com-
pound. In still other embodiments the substituted hydrocarbon additive of the
present invention includes a combination of two or more of the additives de-
scribed 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 ployalkcncs 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
polyolfincs.
[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
character-
ized 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 intcrpolymers of poly-
merizable 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,
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CA 3025740 2018-11-29
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. Patent
4,234,435.
[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 2Ø 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-
Date Recue/Date Received 2021-02-18
heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene, 1-docosene,
1-tetra-
cosene, etc. Commercially available alpha-olefin fractions that may be used
include the C15-
18 alpha-olefins, C12-16 alpha-olefins, C14-16 alpha-olefins, C14-18 alpha-
olefins, C16-18 alpha-
olefins, C16-20 alpha-olefins, C22-28 alpha-olefins, etc. In one embodiment,
the olefins are C16
and C16-18 alpha-olefins. Additionally, C30+ 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 to about
130 C until the desired degree of isomerization is achieved. These procedures
are described
for example in U.S. 4,108,889.
[0028] The mono-olefins may be derived from the cracking of paraffin wax.
The wax
cracking process yields both even and odd number C6-20 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 C6-20 liquid
olefins, obtained from the wax cracking process, yields fractions (e.g., C15-
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.
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Date Recue/Date Received 2021-02-18
[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 , or about
185 C up to about 240 C, or to about 210 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.
Patent
3,412,111; and Ben et al, "The Ene Reaction of Maleic Anhydride With Alkenes",
J.C.S.
Perkin 11 (1977), pages 535-537. 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.
Patents 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.
[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
7
Date Recue/Date Received 2021-02-18
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.
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Date Recue/Date Received 2021-02-18
[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. 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. 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.
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
9
Date Recue/Date Received 2021-02-18
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 C or higher.
In
some embodiments the hydrocarbon solvent is an aromatic naphtha having a
flash point above 62 C or an aromatic naphtha having a flash point of 40 C or
a
kerosene with a 16% aromatic content having a flash point above 62 C.
[0042] Aliphatic hydrocarbons include various naphtha and kerosene
boiling
point fractions that have a majority of aliphatic components. Aromatic hydro-
carbons 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 alco-
hol, and 2-methyl-1-butanol.
[0043] The oxygen containing composition can include an alcohol, a
ketone,
an ester of a carboxylic acid, a glycol andlor 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 composi-
tion 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 com-
bination 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 han-
dling characteristics of the concentrate, such as its viscosity.
CA 3025740 2018-11-29
[0045] In several
embodiments of the invention the fuel composition, fuel
additive concentrate, and/or the fuel additive itself arc 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 composi-
tion, 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 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 composi-
tions 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 embodi-
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CA 3025740 2018-11-29
ments 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
suscepti-
ble 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 com-
position that also comprises a fuel. This fuel may or may not exhibit a propen-
sity 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
con-
taining compositions of the present invention as well as the fuel and/or fuel
additive compositions to which the additive containing compositions may be
added.
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CA 3025740 2018-11-29
[0054] Fuels suitable for use in the present invention are not overly
limited.
Generally, suitable fuels arc normally liquid at ambient conditions e.g., room
temperature (20 to 30 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 hydro-
carbons 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 nitro-
methane.
[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 em-
bodiments is present at greater than 97% by weight, greater than 99.5% by
weight, or greater than 99.9% by weight.
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CA 3025740 2018-11-29
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
condi-
tions under which the engine is being operated.
1100601 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 deriva-
tive 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 dispers-
ants, quaternary salt dispersants, and succinimide dispersants including den-
vales 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
sulfosuccinatc salt.
[0063] Suitable antifoams also include organic silicones such as
polydi-
methyl siloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and
polymethacrylates, trimethyl-triflouro-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)
14
CA 3025740 2018-11-29
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
tricar-
boxylic 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 struc-
ture. Examples of a suitable branched alcohols used to prepare these friction
modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures
thereof.
1100661 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. Patents 4,234,435 and 3,172,892. Such materi-
als may also contain ester linkages or ester functionality.
[0067] Another class of nitrogen-containing dispersant is the Mannich
bases.
These arc 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. Patent
3,634,515.
[0068[ Other nitrogen-containing dispersants include polymeric
dispersant
additives, which are generally hydrocarbon-based polymers which contain
CA 3025740 2018-11-29
nintrogen-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.
10070] 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-subsituted phenol, an aldehyde, and an amine; and
(ii)
a quaternizing agent suitable for converting the tertiary amino group of com-
pound (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 polyal-
kene-substituted amine having at least one tertiary amino group and/or a Man-
nich reaction product having a tertiary amino group; and (ii) a quaternizing
agent.
16
CA 3025740 2018-11-29
[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 em-
bodiments 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 hydro-
carbon, generally a polyolefin substituted with a monounsaturated carboxylic
acid reactant such as (1) monounsaturated C4 to C10 dicarboxylic acid such as
fumaric acid, itaconic acid, malcic acid.; (2) derivatives of (1) such as anhy-
drides or CI to C5 alcohol derived mono- or di-esters of (1); (3) monounsatu-
rated C3 to C10 monocarboxylic acid such as acrylic acid and methacrylic
acid.;
or (iv4 derivatives of (3) such as C1 to C5 alcohol derived esters of (3) with
any
compound containing an olefinic bond represented by the general formula:
(R1)(R1)C=C(R1)(CH(R1)(0) (I)
wherein each R.' 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 C2 to C20, e.g.
C2 to C5 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; butylenc 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 C4 to C18
diolefin, e.g., a copolymer of isobutylene and butadicne; or a copolymer of
ethylene, propylene and 1,4-hexadiene.
[00751 In one embodiment, at least one R of formula (I) is derived
from
polybutene, that is, polymers of C4 olefins, including 1-butene, 2-butene and
isobutylene. C4 polymers can include polyisobutylenc. 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 copoly-
1 7
CA 3025740 2018-11-29
mers and ethylene-lower olefin-diene terpolymers are described in numerous
patent
documents, including European patent publication EP0279863 and the following
United
States patents: 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.
[0076] In another embodiment, the olefinic bonds of formula (I) are
predominantly
vinylidene groups, represented by the following formulas:
-(H)C=C(R2)(R2) (II)
wherein R2 is a hydrocarbyl group, and in some embodiments both R2 groups are
methyl groups,
and
-(H)(R3)C(C(CH3)=CH2) (III)
wherein R3 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, such products are commercially available by BASF, under the
tradename GLISSOPAL and by Texas Petrochemicals LP, under the tradename TPC
11O5TM and TPC 595TM
[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.
[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:
(R4C(0)(R5).C(0))R4 (IV)
and
18
Date Recue/Date Received 2021-02-18
OR4
R4¨C¨(R5)¨C(0)0R4
OH (V)
wherein each R4 is independently H or a hydrocarbyl group, and each R5 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.
[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.
[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:
R6
N ¨X ¨N
R6' R6
(VI)
wherein X is a alkylene group containing about 1 to about 4 carbon atoms; and
wherein each
R6 is independently a hydrocarbyl group, and R6' can be hydrogen or a
hydrocarbyl group.
)17
HO¨X ¨N
NR7
(VII)
wherein X is a alkylene group containing about 1 to about 4 carbon atoms; and
wherein each
R7 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, pentane diamines , hex ane diamines , heptanediamines, di
ethylenetriamine ,
dipropylenetriamine, dibutylenetriamine, triethylenetetraamine,
tetraethylenepentaamine,
pentaethylenehexaamine, hexamethylenetetramine, and bis(hexamethylene)
triamine, the
diaminobenzenes, the diaminopyridines or mixtures thereof. In addition,
nitrogen or oxygen
19
Date Recue/Date Received 2021-02-18
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: dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-
diethyl-
aminopropylamine, 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 -aminopropyeimidazole and 4-
(3 - aminoprop yl)morpholine ,
1 -(2-aminoethyl)pip eridine,
3,3 -diamino-N-methyldipropyl amine ,
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, US 4,253,980, US 3,778,371, US 4,171,959,
US
4,326,973, US 4,338,206, and US 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
Date Recue/Date Received 2021-02-18
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, exacer-
bated 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
21
CA 3025740 2018-11-29
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 inven-
tion, 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 per-
formance 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.
22
CA 3025740 2018-11-29
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
sub-
stituents, 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); hetcro 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
suscep-
tible 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.
23
CA 3025740 2018-11-29
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.
[0094] Example Set 1 ¨ Fuel treated with a succinimide dispersant. An EU
certification diesel fuel, known as RF-06, is treated with 200 ppm of a commer-
cially 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 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 polyisobutylene
succinic anhydride wherein the polyisobutylene has a number
average molecular weight of about 1000, which is not hydro-
lyzed, and which is esterified with 1 equiv of n-butanol.
24
CA 3025740 2018-11-29
[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 2 ¨ Results from Example Set 1.
Sample Additional Additive Zinc Level (ppm) Zinc
Level (ppm)
(at 200 ppm in the Fuel) at 7 Days at 14 Days
1-1 None-Baseline 0.6 1.3
1-2 -moo mw Hydrolyzed PIBSA 0.1 0.1
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 -moo ivtvv Mono Esterified
0.4 0.8
PIBSA
[0096] Example Set 2 - 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 arc
tested in the same manner described above and the results are summarized in
the
table below.
Table 3 ¨ Results from Example Set 2.
Sample Additional Additive Zinc Level (ppm) Zinc
Level (ppm)
(at 500 ppm in the B100) at 7 Days at 14 Days
2-1 None - Baseline 1.5 1.7
2-2 -1000 ivRv Hydrolyzed PIBSA 0.2 0.3
2-3 -550 MW PIBSA 0.3 0.3
2-4 Pentasize 68F 0.2 0.2
2-5 Dimer Acid (hydrogenated) 0.5 0.8
2-6 -1000 MW PIBSA
2_7 -4000 MW Mono Esterified
3.0 3.8
PIBSA
CA 3025740 2018-11-29
[0097] 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 chemi-
cal 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.
26
Date Recue/Date Received 2021-02-18
