BACKGROUND OF THE INVENTION
[0001] Foam control is a highly important consideration in the preparation of additive compositions
for use in fuels of the middle distillate boiling range, such as gas oils, diesel
fuels, gas turbine fuels, burner fuels and the like. If a fuel foams during transfer
from one tank to another, it becomes difficult to control flow rates and volumes.
Similarly, foaming during the filling of fuel tanks can pose various other problems,
such as delivery of inadequate amounts of fuel to the tanks or conversely, overflowing
and spillage of fuel at the filling site.
[0002] To overcome these foaming problems, a variety of foam inhibitors such as polyacrylates
and polysiloxanes have been proposed for use in diesel fuels and additive packages
to be used in formulating finished diesel fuels.
[0003] When producing certain additive concentrates for use in improving the performance
characteristics of middle distillate fuels it has been found necessary to include
a fairly high amount of the foam inhibitor in the concentrates to ensure that the
finished fuel will have a sufficient level of antifoam additive to effectively suppress
or inhibit foam formation in the fuel during operations such as referred to above.
In general, amounts of antifoam additive of at least 0.5% by weight in the additive
concentrate are required. Indeed, amounts as high as 10% by weight or more of foam
inhibitor in the concentrate may be required for effective utilization of some additive
concentrates.
[0004] It has been discovered that when the additive concentrate contains both a high level
of a silicone antifoam agent and an overbased detergent, a serious problem of incompatibility
can arise. This problem is manifested in many ways. For one thing, insoluble sediments
or particulate matter can be generated in the additive concentrate, especially during
storage. Moreover, experimental results indicate that even if the interaction between
the overbased detergent and the silicone antifoam agent does not result in visually
perceptible amounts of solids, nevertheless this incompatibility can cause a significant
loss of antifoam performance in the resultant finished fuel. Concurrent manifestation
of both such adverse consequences is also possible. This incompatibility does not
always occur in compositions containing an antifoam and an overbased detergent. Products,
such as HiTEC® 4043L fuel additive commercially available from Ethyl Corporation,
containing a polyether polysiloxane antifoam which is soluble in water at 25°C, such
as TEGOPREN® 5851 silicone surfactant commercially available from T.H. Goldschmidt
AG, and an overbased calcium sulfonate detergent do not exhibit the above described
incompatibility and are thus not within the purview of this invention.
[0005] European Patent Application No. 0 681 023 discloses fuel additive which comprise
an overbased alkali or alkaline earth metal-containing detergent and a water-soluble
polyether-polysiloxane copolymer as a foam inhibitor. The additive may further comprise
a corrosion inhibitor, a hydrocarbon-soluble ashless dispersant, a diluent and other
conventional additives.
[0006] European Patent Application No. 0 476 196 relates to fuels and additive compositions
which possess improved combustion characteristics, and form products with reduced
acidity. The additives may contain metal-containing basic detergent salts, fuel-soluble
manganese carbonyl compounds, ashless dispersants and other conventional fuel additive
components.
[0007] A need has thus arisen for a way of effectively overcoming the problem of additive
incompatibility as between overbased metal detergents and siloxane foam inhibitors
especially when the latter are used at relatively high concentrations in additive
packages and in resultant fuel compositions.
[0008] It has now been found that the addition of a lubricity additive can substantially
improve the foam behaviour of fuels containing colloidally dispersed metal containing
materials, such as overbased metal detergents or metal based emissions improving additives,
in the presence of a wide range of antifoam agents.
SUMMARY OF THE INVENTION
[0009] According to the present invention there is provided a fuel additive composition
which comprises as components thereof (i) a lubricity additive, (ii) at least one
overbased metal detergent, and (iii) a siloxane antifoam agent which is insoluble
in water at 25°C, and wherein components (i), (ii), and (iii) are present in amounts
such that, when the composition is diluted with a base oil, the following amount of
each component is present:
component (i) |
10-400 ppm |
component (ii) |
1-100 ppm of the metal component |
component (iii) |
1-30 ppm. |
[0010] In one embodiment of the present invention there is provided a fuel additive composition
as above which further comprises (iv) a dispersant and/or (v) a metal based emissions
improving additive, the weight ratio of (iv) to (iii) on an active ingredient basis
is normally in the range of about 0.25 to about 300 parts by weight of (iv) per part
by weight of (iii).
[0011] Other components which may be, and preferably are, included in any of the foregoing
concentrates include a liquid hydrocarbon diluent (especially a liquid highly aromatic
hydrocarbon diluent) or a liquid alcohol diluent or a demulsifying agent or a corrosion
inhibitor, or any mixture of any two or more of the foregoing.
[0012] Still other embodiments include liquid fuel compositions, such as fuels boiling in
the middle distillate boiling range, containing the components in accordance with
any of the foregoing additive concentrates.
[0013] In a further embodiment of the present invention there is provided a method of reducing
foam in fuel compositions containing an overbased metal detergent and a silicone antifoam
agent which is substantially insoluble in water at 25°C, wherein a lubricity additive
is combined with said fuel compositions.
[0014] The above and other embodiments and advantages of this invention will become still
further apparent from the ensuing description and appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
Component (i)
[0015] The lubricity additives of the present invention are preferably carboxylic acids,
optionally substituted with at least one hydroxy group, or derivatives thereof. The
preferred carboxylic acid derivatives are carboxylic acid amides and carboxylic acid
esters.
[0016] The hydroxy-substituted carboxylic acid or acid derivative may be used alone or in
combination with any other hydroxy-substituted acid and/or acid derivative. The hydroxy-substituted
acid used in the present invention typically contains up to 60 carbon atoms. The hydroxy-substituted
acid may be a mono- or poly-carboxylic acid or a dimerized acid. When hydroxy-substituted
mono-carboxylic acids are used they typically contain 10 to 40 carbon atoms, more
commonly 10 to 30 and especially 12 to 24 carbon atoms. The preferred acid of this
type is the fatty acid, ricinoleic acid. When hydroxy-substituted poly-carboxylic
acids are used, such as di- or tri-carboxylic acids, they typically contain 3 to 40
carbon atoms, more commonly 3 to 30 and especially 3 to 24 carbon atoms. Examples
of this kind of hydroxy-substituted poly-carboxylic acid include ricinoleic, malic,
tartaric and citric acids. It is also possible to use as the hydroxy-substituted acid,
dimerized acids. Herein such compounds are referred to as dimer and trimer acids.
When used the dimerized acid typically contains 10 to 60, preferably 20 to 60 and
most preferably 30 to 60, carbon atoms. Such acids are prepared by dimerizing unsaturated
acids and introducing a hydroxyl functionality. Such acids typically consist of a
mixture of monomer, dimer and trimer acid. According to one embodiment of the invention
the acid is a hydroxy-substituted dimerized fatty acid, for example of oleic and linoleic
acids. Typically this dimer exists as a mixture of 2% by weight monomer, 83% by weight
dimer and 15% by weight of trimer and possibly higher acids. The preferred dimer acid,
as well as the other acids described above, are commercially available or may be prepared
by the application or adaptation of known techniques.
[0017] As described above, the lubricity additive compound(s) used may be in the form of
a carboxylic acid derivative. One kind of derivative which may be used is an ester
of the acid with a polyhydric alcohol. The polyhydric alcohol from which the ester
may be derived typically contains from 2 to 7 carbon atoms. Examples of suitable alcohols
include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol
and dipropylene glycol, glycerol, arabitol, sorbitol, mannitol, pentaerythritol, sorbitan,
1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol and 1,2-cyclohexanediol. These
alcohols are readily available. Of the alcohols mentioned it is preferred to use glycerol
or sorbitan. In a preferred embodiment the ester has at least one free hydroxyl group
in the moiety derived from the polyhydric alcohol, i.e. not all of the hydroxyl groups
of the polyhydric alcohol are esterified. The use of glycerol monoricinoleate is particularly
preferred.
[0018] Another carboxylic acid derivative which may be used is the ester of the hydroxy-substituted
acid with an alkanolamine of formula:
R
1[N(R
1)(CH
2)
p]
qY
in which p is 2 to 10, q is 0 to 10, Y is -N(R
1)
2, 4-morpholinyl or 1-piperazinyl N-substituted by a group R
1 or a group -[(CH
2)
pN(R
1)]
qR
1 in which p and q are as defined above and each substituent R
1 is independently selected from alkyl groups having from 1 to 6 carbon atoms and a
group of formula:
-(R
2O)
rR
3
in which r is 0 to 10, R
2 is an alkylene group having 2 to 6 carbon atoms and R
3 is an hydroxyalkyl group having 2 to 6 carbon atoms, provided at least one group
R
1 is -(R
2O)
rR
3. Thus, the alkanolamine is one which does not contain any hydrogen-bearing nitrogen
atoms. The presence of free hydrogen atoms would be expected to lead to the formation
of an amide on reaction with the acid. The alkanolamines which may be used are commercially
available or may be made by the application or adaptation of known methods.
[0019] According to a preferred embodiment, in the alkanolamine of the above formula Y is
-N(R
1)
2, p is 2 and q is 0 to 3. It is further preferred that each R
1 is a C
2-4 hydroxyalkyl group, C
2 or C
3 hydroxyalkyl being particularly preferred. Specific examples of such compounds include
triethanolamine, triisopropylamine and ethylene diamine and diethylene triamine in
which each nitrogen atom is substituted by hydroxyethyl or hydroxypropyl groups.
[0020] In another preferred embodiment, in the alkanolamine Y is 4-morpholinyl or substituted
1-piperazinyl, q is 0 or 1 and p is from 2 to 6. Examples of such alkanolamines include
aminoethylpiperazine, bis-(aminoethyl)piperazine and morpholine, N-substituted by
an hydroxypropyl group.
[0021] The alkanolamines are commercially available or may be made by the application or
adaptation of known techniques.
[0022] It is also possible to use as the carboxylic acid derivative, an amide such as that
formed by reaction of a hydroxy substituted carboxylic acid with ammonia or a nitrogen-containing
compound of formula:
R
1[N(R
1)(CH
2)
p]
qY
in which p is 2 to 10, q is 0 to 10, Y is -N(R
1)
2, 4-morpholinyl or 1-piperazinyl optionally N-substituted by a group R
1 or a group -[(CH
2)
pN(R
1)]
qR
1 in which p and q are as defined above and each substituent R
1 is independently selected from hydrogen and alkyl groups having 1 to 6 carbon atoms
and a group of formula:
-(R
2O)
rR
3
in which r is 0 to 15, R
2 is an alkylene group having 2 to 6 carbon atoms and R
3 is an hydroxyalkyl group having 2 to 6 carbon atoms, provided that at least one group
R
1 is hydrogen.
[0023] According to a preferred embodiment, in the nitrogen- containing compound Y is -N(R
1)
2, p is 2 and q is 0 to 3. Examples of such compounds include diethanolamine, tris(hydroxymethyl)aminomethane,
triethylene tetramine or diethylene triamine optionally N-substituted by two hydroxypropyl
groups.
[0024] In another embodiment, in the nitrogen-containing compound Y is 4-morpholinyl or
optionally N-substituted 1-piperazinyl, p is 2 to 6, q is 0 or 1 and each R
1 is hydrogen. Examples of such compounds include aminoethylpiperazine, bis-(aminoethyl)piperazine
or morpholine.
[0025] The compounds used to form the acid amides are commercially available or may be made
by the application or adaptation of known techniques.
[0026] The alkanolamines and nitrogen-containing compounds of the above formulae in which
r is 1 or more, i.e. those containing an ether or polyether linkage, can be prepared
by reaction of a suitable amine, morpholine or piperazine compound with a molar excess
of one or more alkylene oxides. When the same kind of alkylene oxide is used R
2 and R
3 contain the same alkylene moiety. When different kinds of alkylene oxides are used
R
2 and R
3 may contain the same or different alkylene groups.
[0027] In the formulae for the alkanolamine compound p is 2 to 10, preferably 2 or 3, q
is 0 to 10, preferably 0 to 5 and r is 0 to 15, preferably 0 to 10. When R
1 is alkyl the moiety contains from 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
R
2 is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
R
3 is an hydroxyalkyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
The hydroxyalkyl group typically contains 1 to 3 hydroxy groups. When r is greater
than zero R
3 is typically a mono-hydroxyalkyl group, for example hydroxyethyl or hydroxypropyl.
When r is zero R
3 is typically a mono- or poly-hydroxyalkyl group having up to 4 hydroxyl groups, for
example hydroxyethyl, hydroxypropyl or a 1-hydroxy-2,2-bis(hydroxymethyl)ethyl group.
The values p, q and r take are selected independently. This means for example that
when q is greater than zero, p may take different values in each repeat unit. Also,
when r is greater than zero, R
2 may be the same or different in each ether repeat unit.
[0028] The preferred carboxylic acid amides are oleyl ethanolamide and oleyl diethanolamide.
[0029] The acid used in the present invention which does not contain any hydroxy-substitution
in the acid backbone typically contains up to 60 carbon atoms. The acid may be a mono-
or poly-carboxylic acid or a dimerized acid. When mono-carboxylic acids are used they
typically contain 10 to 40 carbon atoms, more commonly 10 to 30 and especially 12
to 24 carbon atoms. Examples of such include aliphatic fatty acids such as lauric,
myristic, heptadecanoic, palmitic, stearic, oleic, linoleic, linolenic, nonadecanoic,
arachic or behenic acid. Of these the use of oleic acid, linoleic acid or mixtures
of these is preferred. When poly-carboxylic acids are used, such as di- or tri-carboxylic
acids, they typically contain 3 to 40 carbon atoms, more commonly 3 to 30 and especially
3 to 24 carbon atoms. Examples of this kind of poly-carboxylic acid include dicarboxylic
acids such as succinic, glutaric, adipic, suberic, azelaic or sebacic acid, and tricarboxylic
acids such as 1,3,5-cyclohexane tricarboxylic acid and tetracarboxylic acids such
as 1,2,3,4-butane tetracarboxylic acid.
[0030] It is also possible to use as the acid containing no hydroxy substitution in the
backbone, dimerized acids. Herein such compounds are referred to as dimer and trimer
acids. When used the dimerized acid typically contains 10 to 60, preferably 20 to
60 and most preferably 30 to 60, carbon atoms. Such acids are prepared by dimerizing
unsaturated acids and typically consist of a mixture of monomer, dimer and trimer
acid. According to a preferred embodiment of the invention the acid is a dimerized
fatty acid, for example of oleic and linoleic acids. Typically this dimer exists as
a mixture of 2% by weight monomer, 83% by weight dimer and 15% by weight of trimer
and possibly higher acids. The preferred dimer acid, as well as the other acids described
above, are commercially available or may be prepared by the application or adaptation
of known techniques.
[0031] The carboxylic acids containing no hydroxy substitution can be derivatized by reaction
with an alkanolamine. The alkanolamine is typically of formula:
R
1[N(R
1)(CH
2)
p]
qY
in which p is 2 to 10, preferably 2 or 3, q is 0 to 10, preferably 0 to 5, Y is -N(R
1)
2, 4-morpholinyl or 1-piperazinyl N-substituted by a group R
1 or a group -[(CH
2)
pN(R
1)]
qR
1 in which p and q are as defined above and each substituent R
1 is independently selected from alkyl groups having from 1 to 6 carbon atoms, preferably
2 to 4 carbon atoms, and a group of formula:
(R
2O)
rR
3
in which r is 0 to 15, preferably 0 to 10, R
2 is an alkylene group having from 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms,
R
3 is an hydroxyalkyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms,
and provided at least one group R
1 is (R
2O)
rR
3. The hydroxyalkyl group typically contains 1 to 3 hydroxy groups. When r is greater
than zero R
3 is typically a mono-hydroxyalkyl group, for example hydroxyethyl or hydroxypropyl.
When r is zero R
3 is typically a mono- or poly-hydroxyalkyl group having up to 4 hydroxy groups, for
example hydroxyethyl, hydroxypropyl or a 1-hydroxy-2,2-bis(hydroxymethyl)ethyl group.
The values p, q and r take are selected independently. This means for example that
when q is greater than zero, p may take different values in each repeat unit. Also,
when r is greater than zero, R
2 may be the same or different in each ether repeat unit. Thus, the alkanolamine is
one which does not contain any hydrogen-bearing nitrogen atoms. The presence of such
free hydrogen atoms on the nitrogen would be expected to lead to the formation of
an amide on reaction with the fatty acid.
[0032] The alkanolamines which may be used to form the ester are commercially available
or may be made by the application or adaptation of known techniques. For example,
the alkanolamines in which r is 1 or more, i.e. those containing an ether or polyether
linkage, can be prepared by reaction of a suitable amine, morpholine or piperazine
compound with a molar excess of one or more alkylene oxides. When the same kind of
alkylene oxide is used R
2 and R
3 contain the same alkylene moiety. When different kinds of alkylene oxide are used
R
2 and R
3 may contain the same or different alkylene groups.
[0033] According to a preferred embodiment, alkanolamines of the above formula are used
in which Y is -N(R
1)
2, p is 2 and q is 0 to 3. Preferably the alkanolamine is triethanolamine or triisopropylamine
or ethylene diamine or diethylene triamine in which each nitrogen atom is substituted
by hydroxyethyl or hydroxypropyl groups.
[0034] According to an alternative preferred embodiment, in the formula shown above, Y is
4-morpholinyl or substituted 1-piperazinyl, p is 2 to 6 and q is 0 or 1. Examples
of such alkanolamines include aminoethylpiperazine, bis-(aminoethyl)piperazine or
morpholine, N-substituted by an hydyroxypropyl group.
[0035] The esters described may be made by the application or adaptation of known techniques,
or are commercially available ready for use.
[0036] According to one aspect of the present invention, the lubricity enhancing additive
compound is a derivative of the hydroxy-substituted acid and contains at least one
free carboxylic group in the acid-derived moiety. This kind of compound may be formed
using as the starting hydroxy-substituted acid a polycarboxylic acid, for example
a dicarboxylic acid or a dimer or trimer acid. Suitably, the number of moles of the
acid and compound used to form the acid derivative which are reacted is controlled
such that the resulting compound contains at least one free carboxylic functional
group in the acid-derived moiety. For example, if an acid having two carboxylic functions
is used, such as a dicarboxylic or dimer acid, the mole ratio should be about 1:1.
[0037] According to another aspect of the present invention, the ester contains at least
one free carboxylic group in the acid-derived moiety and no hydroxy substitution in
the acid backbone. This kind of compound may be formed using as the starting acid
a polycarboxylic acid, for example a dicarboxylic acid or a dimer or trimer acid.
Suitably, the number of moles of acid and alkanolamine which are reacted is controlled
such that the resulting ester contains at least one free carboxylic functional group
in the acid derived-moiety. For example, if an acid having two carboxyl functions
is used, such as a dicarboxylic or dimer acid, the mole ratio could be about 1:1.
[0038] In the case that the acid derivative contains at least one free carboxylic group
in the acid moiety, it may be used as is or it may be derivatised further to enhance
its properties. The kind of compound used to do this usually depends upon the kind
of acid used initially and the properties of the acid derivative it is desired to
influence. For example, it is possible to increase the fuel solubility of the acid
derivative by introducing into its molecule a fuel-solubilizing species. As an example
of such, long-chain alkyl or alkenyl may be mentioned. To this end the acid derivative
may be reacted with an alcohol, ROH or an amine, RNH
2 in which R is alkyl or alkenyl having up to 30 carbon atoms, for example 4 to 30
carbon atoms. The number of carbon atoms in the alkyl or alkenyl group may depend
upon the number of carbon atoms in the acid derivative itself. These compounds react
with the free carboxylic functional group(s) of the acid derivative to form a further
ester linkage or an amide linkage. Examples of particular alcohols and amides which
may be used include oleyl alcohols and oleyl amine. Alternatively, it is possible
to further react the acid derivative to introduce into its molecule one or more polar
head groups. This has the result of increasing the lubricity enhancing effect which
the acid derivative exhibits. This is believed to be due to the polar head group increasing
the affinity of the acid derivative to metal surfaces. Examples of compounds which
may be used to introduce one or more polar head groups include polyamines (e.g. ethylene
diamine and diethylene triamine), monohydric alcohols (e.g., ethanol and propanol)
and alkanolamines and polyhydric alcohols such as those described above.
[0039] Typically, unless the carboxylic acid derivative is one derived from a dimer or trimer
acid, the derivative is further reacted to introduce fuel-solubilising species. Dimer
and trimer acid derivatives tend already to contain in the acid backbone long chain
alkyl or alkenyl moieties sufficient to provide adequate fuel-solubility.
[0040] While it has been described above that it is the acid derivative which is reacted
further, it is quite possible that the same final species can be formed by first reacting
free carboxylic functional group(s) of a polycarboxylic acid to introduce fuel-solubilising
or polar head groups and then reacting the resultant product to form the acid derivative.
Of course, this assumes that the product formed after the initial reaction contains
at least one free carboxylic group in the acid-derived moiety such that acid derivative
formation is still possible.
Component (ii)
[0041] The metal containing detergents are exemplified by oil-soluble overbased salts of
alkali or alkaline earth metals with one or more of the following acidic substances
(or mixtures thereof): (1) sulfonic acids, (2) carboxylic acids, (3) alkylphenols,
(4) sulfurized alkylphenols, and (5) organic phosphorus acids characterized by at
least one direct carbon-to-phosphorus linkage. Such organic phosphorus acids include
those prepared by the treatment of an olefin polymer (e.g., polyisobutylene) with
a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus
pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,
or phosphorothioic chloride. The most commonly used salts of the above acids are those
of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
[0042] The metal additives are preferably oil-soluble overbased salts of alkali or alkaline
earth metals. The overbased salts are preferred as a means to add metals in a concentrated,
hence cost effective, form but the metals need not be added in this form. The term
"overbased" is used to designate metal salts wherein the metal is present in stoichiometrically
larger amounts than the organic acid radical. This includes low base detergents (i.e.,
those having a TBN of about 6 to 40), as well as high base (i.e., those having a TBN
of about 250 to 500) materials. The commonly employed methods for preparing the overbased
salts involve heating a mineral oil solution of an acid with a stoichiometric excess
of a metal neutralizing agent such metal oxide, hydroxide, carbonate, bicarbonate,
or sulfide, carbonating the mixture in the presence of a promoter, and filtering the
resulting mass. Examples of compounds useful as the promoter include phenolic substances
such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation
products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol,
octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl
alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine,
and dodecylamine. A particularly effective method for preparing the overbased salts
comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing
agent and at least one suitable promoter, and carbonating the mixture at an elevated
temperature such as 60°-200°C.
[0043] Examples of overbased sulfonates include overbased lithium sulfonates, sodium sulfonates,
potassium sulfonates, calcium sulfonates, and magnesium sulfonates wherein each sulfonate
moiety is attached to an aromatic nucleus which in turn usually contains one or more
aliphatic substituents to impart hydrocarbon solubility.
[0044] The metal carboxylates may be derived from any organic carboxylic acid. The metal
carboxylates are preferably those of a monocarboxylic acid such as that having from
about 4 to 30 carbon atoms. Such acids can be hydrocarbon aliphatic, alicyclic, or
aromatic carboxylic acids. Monocarboxylic acids such as those of aliphatic acids having
about 4 to 18 carbon atoms are preferred, particularly those having an alkyl group
of about 6 to 18 carbon atoms. The alicyclic acids may generally contain from 4 to
12 carbon atoms. The aromatic acids may generally contain one or two fused rings and
contain from 7 to 14 carbon atoms wherein the carboxyl group may or may not be attached
to the ring. The carboxylic acid can be a saturated or unsaturated fatty acid having
from about 4 to 18 carbon atoms. Examples of some carboxylic acids that may be used
to prepare the metal carboxylates include: butyric acid; valeric acid; caproic acid;
heptanoic acid; cyclohexanecarboxylic acid; cyclodecanoic acid; naphthenic acid; phenyl
acetic acid; 2-methylhexanoic acid; 2-ethylhexanoic acid; suberic acid; octanoic acid;
nonanoic acid; decanoic acid; undecanoic acid; lauric acid; tridecanoic acid; myristic
acid; pentadecanoic acid; palmitic acid; linolenic acid; heptadecanoic acid; stearic
acid; oleic acid; nonadecanoic acid; eicosanoic acid; heneicosanoic acid; docosanoic
acid; and erucic acid.
[0045] The most preferred carboxylic acids, for preparing the oil-soluble salts of the present
invention, are salicylic acids. Overbased salicylate are exemplified by lithium salicylates,
sodium salicylates, potassium salicylates, calcium salicylates, and magnesium salicylates
wherein the aromatic moiety is usually substituted by one or more aliphatic substituents
to impart hydrocarbon solubility.
[0046] Examples of suitable overbased metal-containing phenate detergents include, but are
not limited to, such substances as overbased lithium phenates, sodium phenates, potassium
phenates, calcium phenates, magnesium phenates, sulfurized lithium phenates, sulfurized
sodium phenates, sulfurized potassium phenates, sulfurized calcium phenates, and sulfurized
magnesium phenates wherein each aromatic group has one or more aliphatic groups to
impart hydrocarbon solubility. The foregoing overbased metal detergents are often
referred to as "overbased phenates" or "overbased sulfurized phenates".
[0047] Also suitable, though less preferred, are (a) the overbased lithium, sodium, potassium,
calcium, and magnesium salts of hydrolyzed phospho-sulfurized olefins having 10 to
2000 carbon atoms or of hydrolyzed phospho-sulfurized alcohols and/or aliphatic-substituted
phenolic compounds having 10 to 2000 carbon atoms. Other similar overbased alkali
and alkaline earth metal salts of oil-soluble organic acids are suitable, such as
the overbased aliphatic sulfonate salts, often referred to as "petroleum sulfonates".
Mixtures of salts of two or more different overbased alkali and/or alkaline earth
metals can be used. Likewise, salts of mixtures of two or more different acids or
two or more different types of acids (e.g., one or more overbased calcium phenates
with one or more calcium sulfonates) can also be used. While rubidium, cesium and
strontium salts are feasible, their expense renders them impractical for most uses.
Likewise, while barium salts are effective, the status of barium as a heavy metal
under a toxicological cloud renders barium salts less preferred for present day usage.
[0048] The metal containing detergent may be of the low base or high base type or mixtures
thereof. Low base detergents have a total base number of greater than about 8, but
less than about 200. Preferred metal containing detergents are high base calcium and
magnesium sulfonates, sulfurized phenates and salicylates having a total base number
(TBN) per ASTM D 2896-88 of at least 200, and preferably above 250.
Component (iii)
[0049] The foam inhibitors useful in the present invention include those antifoam additives
conventionally used in fuel compositions, such as silicone antifoam agents. The advantages
of the present invention are particularly evident when the antifoam used is one which
exhibits a serious incompatibility with the overbased metal detergents. Incompatibility
with the overbased metal detergents is evidenced by severe foaming upon combining
the antifoam and the detergent. This incompatibility is most often seen where the
antifoam agent is one that is largely insoluble in water at 25°C. This problem is
solved by the addition of a lubricity additive of the type described above.
[0050] Preferred antifoam agents are polyether polysiloxane copolymers of the formula
![](https://data.epo.org/publication-server/image?imagePath=2002/19/DOC/EPNWB1/EP98301109NWB1/imgb0001)
wherein R is independently selected from the group consisting of H, OH, C
1-3 alkyl, polyalkoxy, poly-(alkoxy)-X (wherein X is OH, methyl or an ester), and polyalkoxy
derivatives, in which aromatic, phenolic or phenol derivatives are grafted to the
alkoxy or polyether chain. Polyalkoxy chains typically contain ethoxy or propoxy units,
or mixtures of the two. The polyether polysiloxane copolymers may be organosilicone
terpolymers, such as those containing alkyl phenol or modified alkyl phenol derivatives
and polyethers grafted onto a polysiloxane copolymer. Preferred are the antifoams
which are substantially insoluble in water at 25°C.
[0051] Suitable polyether polysiloxane copolymers for use in the present invention include
S911 antifoam, a polyether polydimethylsiloxane commercially available from Wacker
Chemie GmbH; Dow Corning® Q2-2600 antifoam, a polyether polysiloxane copolymer commercially
available from Dow Corning; and TP325 antifoam, an organosilicone terpolymer commercially
available from OSi Specialties Inc.
[0052] Polyether polysiloxane copolymer antifoams which are not part of this invention include
those which are water soluble at 25°C and do not exhibit serious incompatibility with
overbased metal detergents. Examples of these types of copolymers include TEGOPREN®
5851 silicone surfactant commercially available from T.H. Goldschmidt AG, Essen, Germany.
Antifoams of this specific class do not cause the foam stabilization effect for which
the lubricity additives of the present invention are required as a means of controlling.
Component (iv)
[0053] Among the preferred embodiments of this invention is inclusion in the compositions
of at least one hydrocarbon-soluble dispersant. These dispersants comprise long chain
succinimides, long chain succinic esters, long chain succinic ester-amides, long chain
polyamines and long chain Mannich bases. The long chain of these detergent-dispersants
contains an average of at least 20 carbon atoms, e.g., an average of 30 to 200 or
more carbon atoms. Such long chain substituents are usually derived from polyolefin
oligomers or polymers of suitable number average molecular weights such as about 800,
950, 1200, 1350, 1500, 1700, 2100 or 2300 which in turn are formed by polymerization
or copolymerization of olefin monomers such as propylene, butylenes, isobutylene,
amylenes, mixtures of ethylene and propylene, and the like.
[0054] Methods for the manufacture of such dispersant-detergents suitable for use,
inter alia, as additives for fuel compositions are well known and reported in the literature.
Thus, typical succinimides that can be used are described in published PCT Patent
Application WO 93/06194 and published European Patent Application, Publication No.
0441014 (August 14, 1991). For exemplary disclosures of succinic esters or succinic
ester-amides, one may refer for example to U.S. Pat. Nos. 3,184,474; 3,331,776; 3,381,022;
3,522,179; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800;
3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540. Long chain polyamine
dispersant-detergents are described for example in U.S. Pat. Nos. 3,275,554; 3,394,576;
3,438,757; 3,454,555; 3,565,804; 3,671,511; 3,821,302; and European Patent Publication
No. 382,405. Suitable fuel-soluble Mannich base detergent-dispersants which can be
used are disclosed for example in U.S. Patent Nos. 3,948,619; 3,994,698; and especially
4,231,759.
[0055] One preferred group of dispersant-detergents for use in this invention are succinimides
formed by reaction of a polyisobutenyl succinic anhydride and a polyamine, especially
an ethylene polyamine having an average of 2 to 6 nitrogen atoms per molecule such
as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine,
pentaethylene hexamine, and N-[2-hydroxyethyl)ethylene diamine. In these dispersants,
the polyisobutenyl group preferably has a GPC number average molecular weight in the
range of 750 to 2300, more preferably 800 to 1350.
[0056] Also preferred are the Mannich base dispersants formed by reaction of (i) an alkylphenol
in which the alkyl group is derived from a olefin polymer that has a number average
molecular weight in the range of 750 to 2300, preferably 800 to 1350 and most preferably
800 to 1100, (ii) polyalkylene polyamine and (iii) formaldehyde or a formaldehyde
precursor. Most preferably, the alkyl group of the alkylphenol is derived from polypropene
having a number average molecular weight in the range of 800 to 1100, and the polyalkylene
polyamine is diethylene triamine. Other useful dispersants are referred to, for example,
in EP 476,196 B1.
Component (v)
[0057] Additional materials which can be included in the compositions of this invention
are metal based emissions improving additives such as cyclopentadienyl manganese tricarbonyl
compounds. Such compounds, when present in the finished fuels, may contribute to reduction
of exhaust emissions, particularly emission of particulates and smoke. In addition,
use of the cyclopentadienyl manganese tricarbonyl compounds in the compositions of
this invention results in further improvements in induction system cleanliness, particularly
cleanliness of inlet valves. Cyclopentadienyl manganese tricarbonyl compounds which
can be used in the practice of this invention include cyclopentadienyl manganese tricarbonyl,
methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl,
trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese
tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl
manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl
manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl
manganese tricarbonyl, octylcyclopentadienyl manganese tricarbonyl, dodecylcyclopentadienyl
manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, indenyl
manganese tricarbonyl, and the like, including mixtures of two or more such compounds.
Preferred are the cyclopentadienyl manganese tricarbonyls which are liquid at room
temperature such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl
manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and
methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese
tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc. Preparation of such
compounds is described in the literature, for example, U.S. 2,818,417.
[0058] Although less preferred, other fuel-soluble or fuel-dispersible manganese compounds
may be included in the compositions of this invention. These compounds are illustrated
by manganese oleate, manganese naphthenates, manganese octylacetoacetate and manganese
ethylene diamine tetracetate.
[0059] In principle, the advantages of this invention may be achieved in any liquid fuel
derived from petroleum, biomass, coal, shale and/or tar sands. In most instances,
at least under present circumstances, the base fuels will be derived primarily, if
not exclusively, from petroleum.
[0060] The invention is thus applicable to such fuels as kerosene, jet fuel, aviation fuel,
diesel fuel, home heating oil, light cycle oil, heavy cycle oil, light gas oil, heavy
gas oil, bunker fuels, residual fuel oils, ultra heavy fuel oils, and in general,
any liquid (or flowable) product suitable for combustion either in an engine (e.g.,
diesel fuel, gas turbine fuels, etc.) or in a burner apparatus. Other suitable fuels
include liquid fuels derived from biomass, such as vegetable oils (e.g., rapeseed
oil, jojoba oil, cottonseed oil, etc.) or refuse-derived liquid fuels such as fuels
derived from municipal and/or industrial wastes.
[0061] In general, the components of the additive compositions are employed in the fuels
in minor amounts sufficient to improve the combustion characteristics and properties
of the base fuel in which they are employed. The amounts will thus vary in accordance
with such factors as base fuel type and service conditions for which the finished
fuel is intended. However, generally speaking, the following concentrations (ppm)
of the components (active ingredients) in the base fuels are illustrative:
|
General Range |
Preferred Range |
Particularly Preferred Range |
Component (i) Lubricity Additive |
10 to 400 |
15 to 200 |
20 to 100 |
Component (ii) Metal Detergent |
1 to 100 ppm of the metal component |
5 to 50 ppm of the metal component |
10 to 30 ppm of the metal component |
Component (iii) Antifoam Agent |
1 to 30 |
2 to 15 |
3 to 8 |
[0062] In the case of fuels additionally containing one or more of components (iv) and (v),
the following concentrations (ppm) of active ingredients are typical:
|
General Range |
Preferred Range |
Particularly Preferred Range |
Component (iv) Dispersant |
10 to 500 |
20 to 200 |
40 to 100 |
Component (v) Metal Based Emissions Improver |
0.1 to 50 ppm of the metal |
1 to 10 ppm of the metal |
2 to 10 ppm of the metal |
[0063] It will be appreciated that the individual components (i), (ii), and (iii), and also
(iv) and/or (v), if used, can be separately blended into the fuel or can be blended
therein in various subcombinations, if desired. Ordinarily, the particular sequence
of such blending steps is not critical. Moreover, such components can be blended in
the form of a solution or diluent. It is preferable, however, to blend the components
used in the form of an additive concentrate of this invention, as this simplifies
the blending operations, reduces the likelihood of blending errors, and takes advantage
of the compatibility and solubility characteristics afforded by the overall concentrate.
Such a concentrate forms part of the present invention and typically comprises from
99 to 1% by weight additive and from 1 to 99% by weight of solvent or diluent for
the additive which solvent or diluent is miscible and/or capable of dissolving in
the fuel in which the concentrate is to be used. The solvent or diluent may, of course,
be the fuel itself. However, examples of other solvents or diluents include white
spirit, kerosene, alcohols (e.g., 2-ethyl hexanol, isopropanol and isodecanol), aromatic
solvents (e.g., toluene and xylene) and cetane improvers (e.g., 2-ethyl hexylnitrate).
These may be used alone or as mixtures.
[0064] The compositions of the present invention may further contain optional components
conventionally used in fuel compositions such as fuel stabilizers, cetane number improvers,
anti-icers, combustion modifiers, cold flow improvers, antistatic additives, biocides,
antioxidants, corrosion inhibitors, wax antisettling additives and metal deactivators.
[0065] The various optional components that can be included in the fuel compositions of
this invention are used in conventional amounts. Thus, the amounts of such optional
components are not critical to the practice of the present invention. The amounts
used in any particular case are sufficient to provide the desired functional property
to the fuel composition, and such amounts are well known to those skilled in the art.
[0066] The invention is illustrated by the following examples.
EXAMPLES
[0067] The basic formulation for Examples 1 and 2, and Comparative Examples 1-4, excluding
the antifoam and lubricity additives listed in Table 2, is set forth below. The amounts
are based on ml of additive per 1000 ml of fuel.
Table 1.
Basic Formulation |
grams in mix |
weight % |
Solvent1 |
250.77 |
50.14 |
Demulsifier2 |
4.62 |
0.92 |
Corrosion Inhibitor3 |
4.12 |
0.82 |
Metal Detergent4 |
149.02 |
29.8 |
Dispersant5 |
71.02 |
14.2 |
MMT/LP626 |
20.55 |
4.11 |
1: 2-ethyl hexanol. |
2: OFRIC® D5021 demulsifier, commercially available from Baker Performance Chemical. |
3: HiTEC® 536 corrosion inhibitor, low molecular weight succinimide/amide of polyalkylene
polyamine commercially available from Ethyl Corporation. |
4: HiTEC® 611 detergent, an overbased calcium alkyl benzene sulfonate having a nominal
total base number of about 300, commercially available from Ethyl Corporation. |
5: Ashless polyisobutylene succinimide dispersant based on 950 number average molecular
weight polyisobutylene, succinic anhydride and tetraethylene pentamine. |
6: Cyclopentadienyl manganese tricarbonyl compound in xylene/heptane solvent mix. |
[0068] All treated fuels were treated with additive such that this basic formulation would
be present at approximately 0.44 ml of formulation per 1000 ml of fuel.
[0069] To evaluate the various additives and their effects on fuel compositions, foam volume
and time to first spot of fuel surface which was clear of foam were measured. Lower
foam volumes and shorter times to first spot represent improved antifoam behavior.
The base fuel used in the present examples is a low sulfur (< 0.05% by weight of sulfur)
diesel fuel.
[0070] Measured quantities of the lubricity additive and different antifoam agents were
added to separate portions of the basic formulation and the resultant additive concentrates
were then blended into the base fuel to produce fuel compositions which in each case
contained an amount of the additive concentrate equivalent to approximately 0.44 ml/1000
ml of fuel of the basic formulation along with a specified amount of the antifoam
agent and lubricity additive which had been included in the package. The respective
fuels were then promptly shaken under controlled conditions, and in each instance
the time needed for the foam to dissipate was measured. The procedure involved use
of graduated glass cylinders, as employed in ASTM D 1094, that had been cleaned in
chromic acid for a minimum of one hour, rinsed with water followed by acetone and
then dried. The cylinders were filled to the 100 mL mark with fuel. They were then
stoppered and shaken for 1 minute at 2-3 strokes per second, each stroke being 15
to 30 cm long and in a vertical plane. The shaken cylinders were then placed on a
level surface, free from vibration, and the maximum foam volume (ml of foam), and
the time for the first clear point of fuel to form (time (sec) to first spot) were
recorded.
[0071] The results in Table 2 indicate that the fuel additive compositions of the present
invention (Examples 1 and 2) provide fuel compositions which exhibit significantly
reduced foam volume and time to first spot compared to compositions containing only
base fuel (Comparative Example 5), or fuel compositions containing additive mixtures
outside the scope of the present invention (Comparative Examples 1-4) as is evidenced
by the significantly lower values for the foam volume and time to first spot tests
obtained in Examples 1 and 2.
Table 2.
|
Antifoam System |
Amount Antifoam ml/1000 ml fuel |
Amount H26587present ml/1000 ml fuel |
Foam Volume (ml) |
Time to First Spot (sec) |
Example 1 |
S9118 |
0.011 |
0.045 |
1.7 |
15.7 |
Comparative Example 1 |
S911 |
0.011 |
0 |
40 |
>900 |
Example 2 |
Q2-26009 |
0.011 |
0.045 |
3 |
13 |
Comparative Example 2 |
Q2-2600 |
0.011 |
0 |
40 |
>1560 |
Comparative Example 3 |
no antifoam |
0 |
0.045 |
33.3 |
32.3 |
Comparative Example 4 |
no antifoam |
0 |
0 |
33.3 |
34 |
Comparative Example 5 |
Base fuel Only |
0 |
0 |
33 |
28 |
7: HiTEC® 2658 lubricity additive, oleyl diethanolamide commercially available from
Ethyl Corporation. |
8: S911 antifoam, a silicone antifoam agent commercially available from Wacker Chemie
GmbH. |
9: Q2-2600 antifoam, a silicone antifoam commercially available from Dow Corning. |
[0072] Table 3 demonstrates the beneficial effects on foam properties obtained by the addition
of a fatty acid lubricity additive to a system containing an antifoam and an overbased
detergent.
[0073] The results in Table 3 indicate that the fuel additive compositions of the present
invention (Example 3) provide fuel compositions which exhibit significantly reduced
foam volume and time to first spot compared to compositions containing additive mixtures
outside
Table 3.
Components |
Example 3 |
Comparative Example 6 |
Solvent1 |
24.4g |
20.83g |
Metal Detergent4 |
17.86g |
20.3g |
Antifoam8 |
1.63g |
1.87g |
Lubricity Additive10 |
6.09g |
--- |
Treat rate: volume added to fuel |
0.41 ml of formulation per 1000 ml of fuel |
0.36 ml of formulation per 1000 ml of fuel |
Foam Decay Time to first spot(s) |
25.7 sec |
>11 minutes |
Foam volume/ml |
8.7 ml |
30 ml |
10: Oleic acid obtained from the Aldrich Chemical Company. |
the scope of the present invention (Comparative Example 6) as is evidenced by the
significantly lower values for the foam volume and time to first spot tests obtained
in Example 3.
[0074] This invention is susceptible to considerable variation in its practice. Accordingly,
this invention is not limited to the specific exemplifications set forth hereinabove.