Note: Descriptions are shown in the official language in which they were submitted.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
Fuel Oil Compositions
This invention relates to improved oil compositions and improved additive
concentrates therefor, in particular to fuel oil compositions having improved
lubricity
s properties and to additives enhancing a variety of fuel properties and
providing
operational advantages for fuel manufacturers and users.
Concern for the environment has resulted in moves to significantly reduce the
noxious components in emissions when fuel oils are burnt, particularly in
engines
~o such as diesel engines. Attempts are being made, for example, to minimise
sulphur
dioxide emissions. As a consequence attempts are being made to minimise the
sulphur content of fuel oils. Additional refining of fuel oils, necessary to
achieve
these low sulphur levels, often results in reductions in the level of polar
components.
In addition, refinery processes can reduce the level of polynuclear aromatic
is compounds present in such fuel oils.
Reducing the level of one or more of the sulphur, polynuclear aromatic or
polar
components of diesel fuel oil can reduce the ability of the oil to lubricate
the injection
system of the engine so that, for example, the fuel injection pump of the
engine fails
2o relatively early in the life of an engine. The problem of poor lubricity in
diesel fuel oils
is likely to be exacerbated by the future engine developments aimed at further
reducing emissions, which will have more exacting lubricity requirements than
present engines. Similarly, poor lubricity can lead to wear problems in other
mechanical devices dependent for lubrication on the natural lubricity of fuel
oil.
2s
Further, many oil, and particularly fuel oil, compositions suffer from the
problem of
reduced flowability and/or filterability at low temperatures, due to the
precipitation of
the heavier alkanes (and particularly n-alkanes) inherent in such oils. This
problem
of alkane crystallisation at low temperatures is well known in the art.
Additive
3o solutions to this problem have been proposed for many years, in particular,
copolymers of ethylene and vinyl esters such as vinyl acetate or vinyl
propionate
CA 02403793 2002-09-19
WO 01/79397 PC'T/EPO1/04177
2
have been successfully used in commercial applications and are well documented
in
the patent literature.
The problem of poor low temperature filterability has conventionally been
measured
s by the Cold Filter Plugging Point ("CFPP") test, which determines the ease
with which
fuel moves under suction through a filter grade representative of field
equipment.
In recent years, other fuel performance requirements have grown in importance.
In
particular, the degree of settling of precipitating n-alkane crystals has an
important
~o influence on the tendency of such crystals to interrupt fuel supply. Other
additives,
known as "Wax Anti-Settling Additives", and typically based on oil soluble
polar
nitrogen-containing compounds, have been developed to reduce the rate of
settling
of precipitating n-alkanes and so enhance this aspect of fuel low temperature
behaviour. Such additives are typically used in conjunction with the
conventional
is CFPP enhancing ethylene polymers.
Lubricity additives for fuel oils have been described in the art. WO 94/17160
describes an additive which comprises an ester of a carboxylic acid and an
alcohol
wherein the acid has from 2 to 50 carbon atoms and the alcohol has one or more
2o carbon atoms. Glycerol monooleate is specifically disclosed as an example.
WO 98/16596 discloses certain esters of specific substituted aromatic
carboxylic
acids to show improved lubricity performance.
2s There, however, exists in the art a continual need for additives showing
enhanced
performance over existing materials, due not only to the development of
engines with
more exacting performance, but also to the general demand from consumers and
fuel
producers for higher quality fuels.
3o It has now been unexpectedly found that certain esters of aromatic
carboxylic acids
provide improved lubricity performance to fuel oil, particularly at lower
treat-rates,
when used in combination with at least one aromatic condensate or at least one
CA 02403793 2002-09-19
WO 01/79397 PCT/EPOI/04177
3
ethylene polymer or a mixture of both. Such additive combinations may show
performance better than that predicted from their individual properties.
Further, the low temperature properties of a fuel oil can be maintained or
even
s enhanced by addition thereto of certain esters of aromatic carboxylic acids
without
increasing the overall additive treat-rate.
In a first aspect, this invention provides a fuel oil composition comprising,
or
obtainable by admixing, a major amount of a fuel oil and minor amounts of,
(I) one or more compounds having at least one aromatic ring system,
wherein at least one ring system bears, as substituents,
(a) one or more hydroxyl groups or derivatives thereof or both; and
(b) one or more ester groups of the formula
is O
C - O R'
where R' represents a hydrocarbyl group having at least one
2o hydroxyl group or derivatives thereof or both;
(II) one or more aromatic condensates other than those defined in (I) or one
or more ethylene polymers or both; and
(III) optionally, one or more oil-soluble polar nitrogen compounds.
2s In a second aspect, this invention provides an additive composition
comprising, or
obtainable by admixing, (I), (II) and optionally (I II) as defined under the
first aspect.
In a third aspect, this invention provides an additive concentrate comprising,
or
obtainable by admixing, either the additive composition of the second aspect
or (I),
30 (II) and optionally (III) as defined under the first aspect, and a
compatible solvent
therefor.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
4
In a fourth aspect, this invention provides a fuel oil composition obtainable
by
admixing a fuel oil and either the additive composition of the second aspect
or the
additive concentrate of the third aspect.
s In particular, the compounds defined under the first aspect of the invention
provide,
upon addition to low sulfur fuel oils an improvement in fuel lubricity which
can exceed
that obtainable from existing lubricity additives, especially mixtures of the
individual
esters disclosed in WO 94/17160.
~o Gasoline fuels are also subject to compositional constraints, including
restrictions on
the sulfur content, in an effort to reduce pollutants. The principle concern
is the effect
of sulfur on exhaust catalyst life and performance. The lubricity requirements
of
gasoline are somewhat lower than for diesel fuel since the majority of
gasoline fuel
injection systems inject fuel upstream of the inlet valves and thus operate at
much
~s lower pressures than diesel pumps. However, as automobile manufacturers
desire to
have electrically powered fuel pumps within the fuel tanks, failure of these
pumps can
be expensive to repair. These problems are also likely to increase as
injection
systems become more sophisticated and gasoline fuels become more highly
refined.
2o Additional pump wear concerns have arisen with the introduction of vehicles
having
gasoline direct injection engines since the fuel pumps for these vehicles
operate at
significantly higher pressures than traditional gasoline fuel pumps.
Another area subject to pump wear and failure is the use of submerged fuel
pumps in
2s gasoline or diesel engine fuel storage tanks. It is important to reduce the
wear of
these submerged pumps due to the difficulty of getting to these pumps for
repair and
maintenance.
Many commercially available gasoline fuels contain gasoline detergents such as
3o polyisobutylene amine and polyether amine. These compounds are known to
have a
minor effect on the wear properties of these fuels. A growing number of
commercially available gasoline fuels contain oxygenates, such as
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
methyltertiarybutylether (MTBE). These oxygenates are known to increase rates
of
wear of fuel pump components as they have very high friction coefficients.
Also there has been considerable effort in recent years to improve the fuel
economy
s of motor vehicles. One approach to reducing fuel consumption has been
development of additives which reduce engine friction in the combustion
chamber of
an internal combustion engines and thus reduce energy requirements.
In light of the desire for more highly refined fuels, lower sulfur content and
~o oxygenation of the fuels and fuel oil compositions demonstrating improved
fuel
economy, there is a continuing need for lubricity improvers.
An advantage of the present invention is that the lubricity additive does not
adversely
impact upon activity of other additives, such as detergents. Indeed, the
lubricity
is additive of the present invention has been found to minimise undesirable
properties,
such as inlet valve deposits, compared to other lubricity additives.
Accordingly, in a fifth aspect, this invention provides a fuel oil composition
comprising, or obtainable by admixing, a major amount of hydrocarbons boiling
in the
2o gasoline range and minor amounts of (I) as defined in the first aspect, and
optionally
one or more gasoline co-additives selected from anti-knock agents, lead
scavengers,
detergents, dispersants, antioxidants, metal deactivators and carburetor or
fuel
injector detergents.
2s In a sixth aspect, this invention provides an additive composition
comprising, or
obtainable by admixing, (I) as defined in the first aspect and optionally one
or more
gasoline co-additives selected from anti-knock agents, lead scavengers,
detergents,
dispersants, antioxidants, metal deactivators and carburetor or fuel injector
detergents.
In a seventh aspect, this invention provides a concentrate comprising, or
obtainable
by admixing, either the additive composition of the sixth aspect or (I) as
defined in the
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
6
first aspect and one or more gasoline co-additives selected from anti-knock
agents,
lead scavengers, detergents, dispersants, antioxidants, metal deactivators and
carburetor or fuel injector detergents, and a compatible solvent therefor.
s In a eighth aspect, this invention provides the use of (I) as defined in the
first aspect
and optionally one or more gasoline co-additives selected from anti-knock
agents,
lead scavengers, detergents, dispersants, antioxidants, metal deactivators and
carburetor or fuel injector detergents for improving the friction of a fuel
composition
comprising a major amount of hydrocarbons boiling in the gasoline range.
to
The aspects of the invention and other advantages of the invention will become
apparent from the following description.
Fuel Oil Composition (First, Fourth and Fifth Aspects)
is The Compounds) (I)
The compound may comprise one or more aromatic ring systems. By 'aromatic ring
system' in this specification is meant a planar cyclic moiety which may be an
aromatic homocyclic, heterocyclic or fused polycyclic assembly or a system
where
two or more such cyclic assemblies are joined to one another and in which the
cyclic
2o assemblies may be the same or different. It is preferred that the or each
aromatic
ring system is system based on heterocylic or homocyclic 5-or 6- membered
rings,
more preferably 6-membered rings and most preferably benzene rings.
The ring atoms in the aromatic system are preferably carbon atoms but may for
2s example include one or more heteroatoms such as N, S, or O in the system in
which
case the compound is a heterocyclic compound.
It is preferred that at least one aromatic ring system of the compound
contains one or
more hydrocarbon groups as substituents, either bonded directly or indirectly
to a ring
3o atom of the aromatic ring system, preferably bonded directly. Preferably,
at least one
of the hydrocarbon groups is capable of imparting fuel oil solubility to the
compound.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
7
Where the compound comprises only one aromatic ring system, it is preferred
that
one of each of the substituents (a) and (b) is present in such a compound.
One, two
or three hydrocarbon substituents may also be present, at least one of which
is
preferably capable of imparting fuel oil solubility to the compound.
s
Where the compound comprises two or more aromatic ring systems, it is
preferred
that at least one of the systems bears substituents (a) and (b). Preferably at
least
one ring system bears one of each substituent (a) and (b).
to Particularly preferred are compounds wherein the or each aromatic ring
system is a
single, 6-membered ring, especially a benzene structure. Most preferably, the
compound comprises a single benzene ring and having one of each of the (a) and
(b)
substituents, wherein substituent (a) is a hydroxyl group.
is By the term hydrocarbon as used in this specification in relation to the
substituent on
the ring system is meant an organic moiety which is composed of hydrogen and
carbon, which is bonded to the rest of the molecule by a carbon atom or atoms
which
unless the context states otherwise, may be aliphatic, including alicyclic,
aromatic or
a combination thereof. It may be substituted or unsubstituted alkyl, aryl or
alkaryl and
2o may optionally contain unsaturation. The organic moiety may also contain
heteroatoms, such as oxygen, nitrogen or sulfur, provided that such
heteroatoms are
insufficient to alter the essentially hydrocarbon character of the
substituent.
It is preferred that the hydrocarbon substituent is aliphatic, for example
alkyl or
2s alkenyl, which may be branched or preferably straight-chain. Straight-chain
alkyl is
preferred.
It is preferable that at least one hydrocarbon substituent be a hydrocarbon
group of
sufficient oleophilic character to impart fuel oil solubility to the compound.
In this
3o respect, it is preferred that at least one hydrocarbon substituent contains
at least 8
carbon atoms, and preferably 10 to 200 carbon atoms. A substituent having 12
to
54, for example 14 to 36 carbon atoms is particularly preferred. Most
preferred are
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
8
alkyl or alkenyl groups containing 12 to 54 carbon atoms, especially straight
chain
alkyl groups. The groups having 14 to 20 carbon atoms are most advantageous.
Substituent (a) is a hydroxyl group or derivative thereof. When a hydroxyl
group, the
s compound may show particularly good performance as an oxidation inhibitor.
Substituent (b) is an ester group, wherein the carbonyl carbon of the ester is
bonded
indirectly, or preferably directly, to a ring atom of the aromatic ring system
and more
preferably to a ring carbon. The ester group is of the formula:
to
O
-C-O-R'
wherein the group - OR' is derivable from the corresponding alcohol HOR',
wherein
R' represents a hydrocarbyl group having at least one hydroxyl group
substituent or
is a derivative thereof or both. Preferably the hydrocarbyl group substituent
has at least
one hydroxyl group.
By the term hydrocarbyl in this specification is meant an organic moiety which
is
composed of hydrogen and carbon and which is bonded to the rest of the
molecule
2o by a carbon atom or atoms and which includes hydrocarbon groups as
hereinbefore
defined in relation to substituents on the ring system, as well as
predominantly-
hydrocarbon groups containing heteroatoms such as O, N or S provided that such
heteroatoms are insufficient to alter the essentially hydrocarbon nature of
the group.
2s Examples of R' include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl,
ethoxyethyl,
and propoxypropyl.
Particularly good results have been achieved when the alcohol HOR' is a
polyhydroxy alcohol, each hydroxyl group being bonded to a different carbon
atom of
3o the alcohol.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
9
The most favoured alcohols are polyhydroxyalcohols giving rise in the compound
to
ester groups comprising hydroxy - substituted alkyl substituents. Suitable
polyhydroxy alcohols are aliphatic, saturated or unsaturated, straight chain
or
s branched alcohols having 2 to 10, preferably 2 to 6, more preferably 2 to 4,
hydroxyl
groups, and having 2 to 90, preferably 2 to 30, more preferably 2 to 12, most
preferably 2 to 5, carbon atoms in the molecule. As examples, the polyhydroxy
alcohol may be a glycol or diol, or a trihydroxy alcohol. Ethylene glycol and
glycerol
are most highly preferred.
io
In the compound, the substituents (a) and (b) are preferably positioned
vicinally on
the aromatic ring system from which they depend. Where the system is
polycyclic
they are preferably positioned vicinally on the same ring of the polycylic
system, for
example in an ortho position to each other, although they may be positioned on
Is different rings. The or each hydrocarbon on the ring system substituent may
be
positioned vicinally to any of the substituents (a) or (b), or in a position
further
removed in the ring system.
The compound may also be of oligomeric structure, such as a series of aromatic
ring
2o systems connected via esterification with polyhydric alcohols, or via
alkylene bridges
produced, for example, by the phenol-formaldehyde type condensation reaction
of
several aromatic ring systems with an aldehyde. Particularly useful are
methylene -
bridged compounds wherein each aromatic ring system is preferably a
homocyclic,
six-membered ring and wherein, more preferably, each ring carries at least one
of
2s each of the substituents (a) and (b).
Preferably, the compound is fuel oil-soluble.
The compound may be prepared by conventional means. Thus, for example, the
3o compound may be prepared by esterification of a precursor compound having
the
requisite aromatic ring system or systems bearing hydrocarbon substituent
and/or
substituent (a) and one or more carboxylic acid substituents, or acylating
derivatives
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
thereof, capable of esterification with compounds having at least one hydroxyl
group
to form substituent (b).
Preferably, the compound is the ethylene glycol or ethylene oxide or glycerol
ester of
s salicylic acid or substituted salicylic acid.
The Aromatic Condensate(s) (II)
The aromatic condensate is obtainable by the condensation reaction between:
to (i) at least one aldehyde or ketone or reactive equivalent thereof, and
(ii) at least one compound comprising one or more aromatic moieties
bearing at least one substituent of the formula -XR'° and at least one
further substituent -R", wherein:
is
- X represents oxygen or sulphur,
- R'° represents hydrogen or moiety bearing at least one
hydrocarbyl group, and
- R" represents a hydrocarbyl group and contains less than 18
carbon atoms when a linear group.
Reactant (i) comprises one or more aldehydes or ketones or reactive
equivalents
2s thereof. By "reactive equivalent" is meant a material which generates an
aldehyde
under the conditions of the condensation reaction or a material which
undergoes the
required condensation reaction to produce moieties equivalent to those
produced by
an aldehyde. Typical reactive equivalents include oligomers or polymers of the
aldehyde, acetals, or aldehyde solutions.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
I1
Particularly preferred reactants (i) are formaldehyde, acetaldehyde, the
butyraldehydes and substituted analogues or reactive equivalents thereof.
Formaldehyde and glyoxylic acid (or pyruvic acid) are particularly preferred.
s Reactant (ii) preferably comprises one or more compounds wherein each
aromatic
moiety bears one substituent of the formula -XR'°. More preferably,
(ii) bears one
substituent of the formula R" and most preferably, also one substituent of the
formula -XR'°. X is preferably oxygen.
to Most preferably, the aromatic moiety is a benzene or substituted benzene
nucleus.
In every aspect of the invention, a preferred Reactant (ii) comprises a
benzene
nucleus bearing one substituent of formula -XR'° and one substituent of
formula R".
Is R'° may represent a moiety bearing a hydrocarbyl group, where
hydrocarbyl is as
defined above in relation to the compound (I). Preferably, the hydrocarbyl
group in
R'° is an aliphatic group, such as alkenyl or alkyl group, which may be
branched or
preferably straight chain. The hydrocarbyl group in R'° may be bonded
directly to the
oxygen or sulphur atom (represented by X in the formula -XR'°) or may
be bonded
2o indirectly by means of a functional group, for example on ester, ether,
peroxide,
anhydride or polysulphide linkage.
Preferably, where R'° is hydrocarbyl, the hydrocarbyl group in
R'° contains 8-40
carbon atoms, more preferably 12-24 carbon atoms, such as 12-18 carbon atoms.
2s Most preferably, R'° is hydrogen.
R" may independently represent those hydrocarbyl groups contemplated as
forming
part of the moiety R'°, although typically R'° and R" (where
both are present) will on
any one aromatic moiety, will be different from each other, and may be the
same or
3o different on different aromatic moieties.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
12
Preferably, R" is an alkenyl or, more preferably, alkyl group, most preferably
containing less than 18 carbon atoms. More preferably, R" is a branched chain
group, preferably an alkyl group. Most preferred embodiments of R" include
branched chain alkyl groups containing less than 16 carbon atoms, for example
4 to
s 16 carbon atoms, such as groups containing 8, 9, 12 or 15 carbon atoms.
Groups
containing 9 carbon atoms are most preferred. Minor amounts of short chain
alkyl
groups (e.g. 4 carbons or less) may be present.
Preferably, the aromatic condensate is a condensate of formaldehyde and
phenol.
to Preferably, the aromatic condensate is formed from a reactant (ii) which
comprises at
least one aliphatic hydrocarbyl-substituted phenol, such as branched chain C9
or C~5
alkyl phenol, for example nonyl phenol.
The aromatic condensate may be combined with at least one amine bearing at
least
Is one hydrocarbyl substituent. Such combination may be purely by admixture,
but is
preferably by physical or chemical associated or complexation. More
preferably, the
aromatic condensate is reacted with at least one amine, more preferably to
form the
amine salt derivative thereof.
2o In a preferred embodiment, the aromatic condensate may be formed by the
reaction
of (i), (ii) and at least one further reactant (iii), wherein reactant (iii)
comprises at least
one compound comprising one or more aromatic moieties bearing at least one
substituent of the formula -XR'° and at least one further substituent -
R'2 wherein:
2s - X represents oxygen or sulphur,
- R'° represents hydrogen or a moiety bearing at least one hydrocarbyl
group,
and
30 - R'2 represents a COOH or S03H group or derivative thereof.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
13
Preferably, reactant (iii) is salicylic acid or a substituted derivative
thereof, or p-
hydroxy-benzoic acid or a substituted derivative thereof.
Preferably the product obtainable from reaction of (i), (ii) and (iii) are
combined with
s at least one amine, as described above. In such products, the amine is
preferably
reacted with the substituents of the formula -R3, e.g. the -COOH or -S03H
groups, so
as to form the amine salt derivatives thereof; although salt formation may
additionally
occur via any -OH substituents.
to Preferred as the aromatic condensate are embodiments obtainable from at
least one
alkyl phenol (i) wherein the alkyl substituent contains no more than 15 carbon
atoms,
formaldehyde or a reactive equivalent thereof, and optionally (iii) salicylic
acid, and
wherein the amine is an alkyl or dialkyl amine, preferably as described above
and
more preferably selected form dihydrogenated tallowamine, dicocoamine, and
is mixtures thereof.
Preferably, the aromatic condensate is fuel-soluble.
Aromatic condensates disclosed in EP-A-0857776, PCT/EP/99/03306 and
2o PCT/EP/99/03308 are within the scope of the present invention.
The Ethylene Polymers) (II)
Each polymer may be a homopolymer or a copolymer of ethylene with another
unsaturated monomer. Suitable co-monomers include hydrocarbon monomers such
2s as propylene, n- and i- butylene and the various a.-olefins known in the
art, such as
decene-1, dodecene-1, tetradecene-1, hexadecene-1 and octadecene-1.
Preferred co-monomers are unsaturated ester or ether monomers, with ester
monomers being more preferred. Thus, an ethylene unsaturated ester copolymer
is
3o preferred.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPOI/04177
14
Preferred ethylene unsaturated ester copolymers have, in addition to units
derived
from ethylene, units of the formula:
-CR5R6-CHR'-
~o
wherein R5 represents hydrogen or methyl, R6 represents -COOR8, wherein R8
represents an alkyl group having from 1-12, preferably 1-9 carbon atoms, which
is a
straight chain, or, if it contains 3 or more carbon atoms, branched, or R6
represents
OOCR9, wherein R9 represents R8 or H, and R' represents H or COORS.
These may comprise a copolymer of ethylene with an ethylenically unsaturated
ester,
or derivatives thereof. An example is a copolymer of ethylene with an ester of
a
saturated alcohol and an unsaturated carboxylic acid, but preferably the ester
is one
of an unsaturated alcohol with a saturated carboxylic acid. An ethylene vinyl
ester
is copolymer is advantageous; an ethylene vinyl acetate, ethylene vinyl
propionate,
ethylene vinyl hexanoate, ethylene vinyl 2-ethylhexanoate, ethylene vinyl
octanoate
or ethylene vinyl versatate copolymer is preferred. Preferably, the copolymer
contains from 5 to 40 wt% of the vinyl ester, more preferably from 10 to 35
wt% vinyl
ester. A mixture of two copolymers, for example as described in US Patent No.
20 3,961,916, may be used. The number average molecular weight of the
copolymer,
as measured by vapour phase osmometry, is advantageously 1,000 to 10,000,
preferably 1,000 to 5,000. If desired, the copolymer may contain units derived
from
additional comonomers, e.g. a terpolymer, tetrapolymer or a higher polymer,
for
example where the additional comonomer is isobutylene or disobutylene, or a
further
2s unsaturated ester.
Within the meaning of this specification, "copolymer" refers to a polymer
obtained
from two or more different co-monomers.
3o Most preferably, the ethylene polymer comprises an ethylene vinyl acetate
or
ethylene vinyl propionate copolymer, or a mixture thereof, or a terpolymer of
ethylene
and two vinyl esters, each giving rise to polymer units corresponding to the
above
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
formula. Particularly preferred are terpolymers of ethylene, vinyl acetate and
a third
unsaturated ester monomer, for example, selected from vinyl propionate, vinyl
2-ethyl
hexanoate, or vinyl versatate.
s Preferably, the ethylene polymer is fuel-soluble.
The Oil Soluble Polar Nitrogen Compounds) (III)
Such compounds carry one or more, preferably two or more, substituents of the
formula >NR'3, where R'3 represents a hydrocarbyl group containing 8-40 carbon
to atoms, which substituent or one or more of which substituents may be in the
form of
a ration derived therefrom. R'3 preferably represents an aliphatic hydrocarbyl
group
containing 12-24 carbon atoms. The oil soluble polar nitrogen compound is
capable
of acting as a wax crystal growth inhibitor in fuels.
is Preferably, the hydrocarbyl group is linear or slightly linear, i.e. it may
have one short
length (1-4 carbon atoms) hydrocarbyl branch. When the substituent is amino,
it may
carry more than one said hydrocarbyl group, which may be the same or
different.
The polar nitrogen compound may comprise one or more amino or imino
2o substituents. More especially, the or each amino or imino substituent is
bonded to a
moiety via an intermediate linking group such as -CO-, -C02(-), -S03(-) or
hydrocarbylene. Where the linking group is anionic, the substituent is part of
a
cationic group, as in an amine salt group.
2s When the polar nitrogen compound carries more than one amino or imino
substituent, the linking groups for each substituent may be the same or
different.
Suitable amino substituents are long chain C~2-C4o, preferably C~2-C24, alkyl
primary,
secondary, tertiary or quaternary amino substituents.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
16
Preferably, the amino substituent is a dialkylamino substituent, which, as
indicated
above, may be in the form of an amine salt thereof; tertiary and quaternary
amines
can form only amine salts. Said alkyl groups may be the same or different.
s Preferred amino substituents are the secondary hydrogenated tallow amino
substituent, the alkyl groups of which are derived from hydrogenated tallow
fat and
are typically composed of approximately 4% C~4, 31 % C~6 and 59% C,8 n-alkyl
groups by weight, and the dicocoamino substituent, composed predominantly of
C~2
and C~4 n-alkyl groups.
to
Suitable imino substituents are long chain C~2-C4o, preferably C~2-C24, alkyl
substituents.
Said polar nitrogen compound is preferably monomeric (cyclic or non-cyclic) or
is aliphatic polymeric, but is preferably monomeric. When non-cyclic, it may
be
obtained from a cyclic precursor such as an anhydride or a spirobislactone.
The cyclic ring system of the compound may include homocyclic, heterocyclic,
or
fused polycyclic assemblies in which the cyclic assemblies may be the same or
2o different. Preferably, the or each cyclic assembly is aromatic, more
preferably a
benzene ring. Most preferably, the cyclic ring system is a single benzene ring
when it
is preferred that the substituents are in the ortho or meta positions, which
benzene
ring may be optionally further substituted.
2s The ring atoms in the cyclic assembly or assemblies are preferably carbon
atoms but
may for example include one or more ring N, S or O atom, in which case or
cases the
compound is a heterocyclic compound.
Examples of polar nitrogen compounds are described below:
(i) Amine salts and/or amides of mono- or poly- carboxylic acids or reactive
equivalents thereof (e.g. anhydrides), e.g. having 1-4 carboxylic acid groups.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
17
Each may be made, for example, by reacting at least one molar proportion of a
hydrocarbyl substituted amine with a molar proportion of the acid or its
anhydride.
s When an amide is formed, the linking group is -CO-; when an amine salt is
formed, the linking group is -COZ(-).
(ii) Polar nitrogen compounds of the general formula:
A~ /X R 20
.C
R21
B
to in which -Y-R2' is S03~-»+1NR3R2', -S03~-»+~HNR222R2',
-SO3~-»+~HZNR22R2', -S03~-»+~H3NR2', -S02NR22R2' or -S03R2'; and -X-R2°
is -Y-
R2' or -CONR22R2°, -COz~-»+>NR223R2°, -C02c-»+~HNR222R2o,
-R23-COOR, -NR22COR2°, _R230R2o, -R2sOCOR2°, _R2s, -R2o -
N(COR22)R2° or
Z~-»+~NR22 3R2°; -Z~-~ is S03~-~ or -C02~-~;
Is
R2° and R2' are alkyl, alkoxyalkyl or polyalkoxyalkyl containing at
least 10 carbon
atoms in the main chain.
R22 is hydrocarbyl and each R22 may be the same or different and R23 is absent
or is
2o C~ to C5 alkylene and in:
A~
C
B /C
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
18
the Carbon-Carbon (C-C) bond is either:
(a) Ethylenically unsaturated when A and B may be alkyl, alkenyl or
substituted hydrocarbyl groups or,
s
(b) Part of a cyclic structure which may be aromatic, polynuclear aromatic or
cyclo-aliphatic,
(iii) Amines or diamine salts of:
to
(a) A sulphosuccinic acid,
(b) An ester or diester of a sulphosuccinic acid,
is (c) An amide or a diamide of a sulphosuccinic acid, or
(d) An ester amide of a sulphosuccinic acid.
(iv) Chemical compounds comprising or including a cyclic ring system, the
2o compound carrying at least two substituents of the general formula (I)
below on the
ring system:
-A-NR25R26 (I)
where A is an aliphatic hydrocarbyl group that is optionally interrupted by
one or more
2s hetero atoms and that is straight chain or branched, and R25 and R26 are
the same or
different and each is independently a hydrocarbyl group containing 9-40 carbon
atoms optionally interrupted by one or more hetero atoms, the substituents
being the
same or different and the compound optionally being in the form of a salt
thereof.
30 (v) A condensate of long chain primary or secondary amine with an aliphatic
carboxylic acid-containing polymer, such as a polymer of malefic anhydride and
one
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
19
or more unsaturated monomers, for example ethylene or another a olefin such as
C6-
C3o a olefin.
Preferred polar nitrogen compounds are those wax anti-settling additives
comprising
s the amides and/or amine salts, or mixtures thereof, of aromatic or aliphatic
polycarboxylic acid (or reactive equivalents thereof) and alkyl or dialkyl
amines, such
as those formed from the following:
(i) Benzene dicarboxylic acids (or anhydrides thereof), such as phthalic
to anhydride.
(ii) Alkylene di- or polyamine tetraacetic or tetra propionic acids, such as
EDTA (Ethylene Diamine Tetraacetic Acid), and
is (iii) Alkyl or alkenyl substituted succinic acids.
The preferred amines include dialkyl amines having 10-30, preferably 12-20
carbon
atoms in each alkyl chain, for example dihydrogenated tallow amine or
dicocamine,
or mixtures thereof.
Compounds resulting from the reaction of phthalic anhydride and dialkyl
amines,
such as those specified above, are most preferred.
Therefore, the nitrogen compound is preferably an amine salt and/amide formed
by
2s reacting at least one molar proportion of a hydrocarbyl-substituted amine
and a molar
proportion of a hydrocarbyl acid having from 1 to 4 carboxylic acid groups or
its
anhydride, such as an amide - amine salt formed by reacting 1 molar portion of
phthalic anhydride with 2 molar proportions of dihydrogenated tallow amine.
3o Preferably, the nitrogen compound is fuel-soluble.
CA 02403793 2002-09-19
WO 01/79397 2p PCT/EPO1/04177
The Fuel Oil
The fuel oil, with respect to the first or fourth aspect, may be a hydrocarbon
fuel such
as a petroleum-based fuel oil for example kerosene or distillate fuel oil,
suitably a
middle distillate fuel oil, i.e: a fuel oil obtained in refining crude oil as
the fraction
s between the lighter kerosene and jet fuels fraction and the heavier fuel oil
fraction.
Such distillate fuel oils generally boil within the range of about
100°C to about 500°C,
e.g. 150° to about 400°C, for example, those having a relatively
high Final Boiling
Point of above 360°C (by ASTM-D86). The fuel oil can comprise
atmospheric
distillate or vacuum distillate, or cracked gas oil or a blend in any
proportion of
~o straight run and thermally and/or catalytically cracked distillates. The
most common
petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils
and heavy
fuel oils, diesel fuels and heating oils being preferred. The diesel fuel or
heating oil
may be a straight atmospheric distillate, or may contain minor amounts, e.g.
up to
35 wt %, of vacuum gas oil or cracked gas oils or both.
is
Also, the fuel oil may be of animal or vegetable oil origin (i.e. a
'biofuel'), or a mineral
oil as described above in combination with one or more biofuels. Biofuels,
being
fuels from animal or vegetable sources, are obtained from a renewable source.
Vl/ithin this specification, the term "biofuel" refers to a vegetable or
animal oil or both
20 or a derivative thereof. Certain derivatives of vegetable oil, for example
of rapeseed
oil, e.g. those obtained by saponification and re-esterification with a
monohydric
alcohol, may be used as a substitute for diesel fuel.
The fuel oil composition has a sulphur concentration of 0.2% by mass or less
based
2s on the mass of the fuel oil composition, and preferably 0.05% or less, more
preferably 0.03% or less, such as 0.01 % or less, most preferably 0.005% or
less and
especially 0.001 % or less. Low sulfur fuels, for example having less than 0.2
% by
mass of sulfur based on the mass of fuel oil, may be made by means and methods
known in the fuel-producing art, such as solvent extraction,
hydrodesulphurisation
3o and sulphuric acid treatment.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
21
Preferred fuel oils have a cetane number of at least 50. The fuel oil may have
a
cetane number of at least 50 prior to the addition of any cetane improver or
the
cetane number of the fuel may be raised to at least 50 by the addition of a
cetane
improver. More preferably, the cetane number of the fuel oil is at least 52.
s
Preferably, the fuel oil is a middle distillate fuel oil, more preferably a
diesel fuel oil.
The fuel oil, with respect to the fifth aspect, will be a fuel boiling in the
gasoline boiling
range, and it may consist substantially of hydrocarbons or it may contain
blending
io components. Alternatively, e.g. in countries such as Brazil, the fuel may
consist
substantially of ethanol.
Suitable liquid hydrocarbon fuels of the gasoline boiling range are mixtures
of
hydrocarbon boiling in the temperature range from about 25°C to about
232°C, and
Is comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and
aromatic
hydrocarbons. Preferred are gasoline mixtures having a saturated hydrocarbon
content ranging from about 40% to about 80% by volume, an olefinic hydrocarbon
content from 0% to about 30% by volume and an aromatic hydrocarbon content
from
about 10% to about 60% by volume. The base fuel is derived from straight run
2o gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins,
synthetically produced aromatic hydrocarbon mixtures, from thermally or
catalytically
reformed hydrocarbons, or from catalytically cracked or thermally cracked
petroleum
stocks, and mixtures of these. The hydrocarbon composition and octane level of
the
base fuel are not critical. The octane level, (R+M)/2, will generally be above
about 85
2s (where R is Research Octane Number and M is Motor Octane Number).
Any conventional base gasoline can be employed in the practice of the present
invention. For example, hydrocarbons in the gasoline can be replaced by up to
a
substantial amount of conventional alcohols or ethers, conventionally known
for use
3o in fuels. The base gasolines are desirably substantially free of water
since water
could impede a smooth combustion.
CA 02403793 2002-09-19
WO 01/79397
PCT/EPOl/04177
22
Normally, the gasolines to which the invention is applied may be leaded or
unleaded,
although are preferably substantially lead-free, and may contain minor amounts
of
one or more blending agents such as methanol, ethanol, tertiary butanol, ethyl
tertiary butyl ether, methyl tertiary butyl ether, and the like, at from about
0.1 % by
s volume to about 25% by volume of the base fuel, although larger amounts
(e.g. up to
40%v) may be utilised.
The fuel oil composition, with respect to the first or fourth aspect, is
preferably
obtained by admixing a fuel oil and additives (I), (I I) and optionally (III),
or the additive
io composition or additive concentrate of the second or third aspect
respectively of the
present invention.
The fuel oil composition, with respect to the fifth aspect, is preferably
obtained by
admixing a fuel oil and additives (I), optionally one or more gasoline co-
additves, or
is the additive composition or additive concentrate of the sixth or seventh
aspect
respectively of the invention.
The Additive Composition (Second and Sixth Aspects
The additive composition is preferably obtained by admixing the additives as
defined
2o under either the first or fifth aspect.
The manufacture of the additive composition may be by methods known in the
art.
The additives, for example (I), (II) and optionally (III), may be blended, for
example
mixed, simultaneously or sequentially at ambient or elevated temperature. The
2s additive composition may further comprise other co-additives (see below).
The Additive Concentrate (Third and Seventh Aspects
The additive concentrate is preferably obtained by admixing, either the
additive
composition of the second or sixth aspect or the additives as defined under
the first
30 or fifth aspect, and a compatible solvent therefor.
Concentrates comprising the additives, for example as the additive
composition, in
admixture with a carrier liquid (e.g. as a solution or a dispersion) are
convenient as a
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
23
means for incorporating the additives into bulk oil such as distillate fuel,
which
incorporation may be done by methods known in the art.
The additives of the invention may be incorporated into bulk oil by other
methods
s such as those known in the art. If co-additives are required, they may be
incorporated into the bulk oil at the same time as the additives of the
invention or at a
different time.
In this specification, the expression "comprising" refers both to compositions
in which
~o the additives, for example (I), (II) and optionally (III), exist discretely
in their individual
forms, and also to compositions in which, after admixing, interaction between
one or
more of the additives (including, where present, further optional additive
components), such as complexation or other in-situ physical or chemical
association
leads to a loss of the discrete identity of the individual additives, but
without
is detracting significantly from the performance of the additives. Similarly,
any of the
compositions of the present invention may be obtained by the admixture of
precursors to additives, for example (I), (II) and (III), and subsequent
reaction to form
the desired additives in-situ in the composition.
2o The terms "fuel- or oil-soluble" or cognate terms, used herein do not
necessarily
indicate that the compounds or additives are soluble, dissolvable, miscible,
or are
capable of being suspended in the fuel oil in all proportions. These do mean,
however, that they are, for instance, soluble or stably dispersible in fuel
oil to an
extent sufficient to exert their intended effect in the environment in which
the fuel is
2s employed. Moreover, the additional incorporation of other additives may
also permit
incorporation of higher levels of a particular additive, if desired.
Preferably, any one of the first to fourth aspects of the present invention
(i.e. fuel oil
composition, or additive composition, or additive concentrate) comprises (I),
(II) and
30 (III); more preferably any one of the first to fourth aspects of the
present invention
comprises one or more compounds (I), one or more aromatic condensates, one or
more ethylene polymers, and one or more oil-soluble polar nitrogen compounds
(III).
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
24
Preferably, any one of the fifth to eighth aspects of the invention comprises
additive
(I) and at least one gasoline co-additive.
s Co-additives
The fuel oil composition, additive composition, or additive concentrate of the
first to
fourth aspects may additionally comprise one or more co-additives useful in
fuel oil
compositions. Such co-additives include other cold flow improving additives,
such as
~o one or more additives selected from the following classes:
(i) comb polymers
(ii) linear ester, ether, ester/ethers and mixtures thereof;
(iii) non-ethylene hydrocarbon polymers, and
Is (iv) hydrocarbylated aromatic compounds.
(i) Generally, comb polymers consist of molecules in which long chain branches
such as hydrocarbyl branches, optionally interrupted with one or more oxygen
atoms
and/or carbonyl groups, having from 12 to 30 such as 14 to 20, carbon atoms,
are
2o pendant from a polymer backbone, said branches being bonded directly or
indirectly
to the backbone. Examples of indirect bonding include bonding via interposed
atoms
or groups, which bonding can include covalent and/or electrovalent bonding
such as
in a salt. Generally, comb polymers are distinguished by having a minimum
molar
proportion of units containing such long chain branches.
Advantageously, the comb polymer is a homopolymer having, or a copolymer at
least
25 and preferably at least 40, more preferably at least 50, molar per cent of
the units
of which have, side chains containing at least 12 atoms, selected from for
example
carbon, nitrogen and oxygen, in a linear chain or a chain containing a small
amount
of branching such as a single methyl branch.
CA 02403793 2002-09-19
WO 01/79397
PCT/EPO1/04177
As examples of preferred comb polymers there may be mentioned those containing
units of the general formula
CDE - CHG CJK - CHL
m n
5
where D represents R3°, COORS°, OCORS°, RS'COORS°
or ORSO;
E represents H, D or RS';
G represents H or D;
J represents H, RS', RS'COORS°, or a substituted or unsubstituted
~o aryl or heterocyclic group;
K represents H, COORS', OCORS', ORS' or COOH;
L represents H, RS', COORS', OCORS' or substituted or
unsubstituted aryl;
RS° representing a hydrocarbyl group having 12 or more carbon
is atoms, and
RS' representing a hydrocarbyl group being divalent in the
RS'COORS° group and otherwise being monovalent,
and m and n represent mole ratios, their sum being 1 and m being finite and
being up
2o to and including 1 and n being from zero to less than 1, preferably m being
within the
range of from 1.0 to 0.4, n being in the range of from 0 to 0.6. RS°
advantageously
represents a hydrocarbyl group with from 12 to 30 carbon atoms, preferably 12
to 24,
more preferably 12 to 18. Preferably, R3" is a linear or slightly branched
alkyl group
and RS' advantageously represents a hydrocarbyl group with from 1 to 30 carbon
2s atoms when monovalent, preferably with 6 or greater, more preferably 10 or
greater,
preferably up to 24, more preferably up to 18 carbon atoms. Preferably, RS',
when
monovalent, is a linear or slightly branched alkyl group. When RS' is
divalent, it is
preferably a methylene or ethylene group. By "slightly branched" is meant
having a
single methyl branch.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
26
The comb polymers may, for example, be copolymers of malefic anhydride or
fumaric
acid and another ethylenically unsaturated monomer, e.g. an a-olefin or an
unsaturated ester, for example, vinyl acetate as described in EP-A-214,786. It
is
preferred but not essential that equimolar amounts of the comonomers be used
s although molar proportions in the range of 2 to 1 and 1 to 2 are suitable.
Examples
of olefins that may be copolymerized with e.g. malefic anhydride, include 1-
dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, and styrene. Other examples of comb
polymer include methacrylates and acrylates.
~o Other suitable comb polymers are the polymers and copolymers of a-olefins
and
esterified copolymers of styrene and malefic anhydride, and esterified
copolymers of
styrene and fumaric acid as described in EP-A-282,342.
Other examples of comb polymers are hydrocarbon polymers such as copolymers of
is ethylene and at least one a-olefin, preferably the a-olefin having at most
20 carbon
atoms, examples being n-dodecene-1, n-tetradecene-1 and n-hexadecene-1 (for
example, as described in W09319106).
(ii) Such compounds comprise an ester, ether, ester/ether compound or mixtures
2o thereof in which at least one substantially linear alkyl group having 10 to
30 carbon
atoms is connected via an optional linking group that may be branched to a non-
polymeric residue, such as an organic residue, to provide at least one linear
chain of
atoms that includes the carbon atoms of said alkyl groups and one or more non-
terminal oxygen, sulphur and/or nitrogen atoms. The linking group may be
polymeric.
By "substantially linear" is meant that the alkyl group is preferably straight
chain, but
that straight chain alkyl groups having a small degree of branching such as in
the
form of a single methyl group branch may be used.
3o The preferred esters, ethers or ester/ethers which may be used may comprise
compounds in which one or more groups (such as 2, 3 or 4 groups) of formula -
ORZs
are bonded to a residue E, where E may for example represent A (alkylene)q,
where
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
27
A represents carbon or nitrogen or is absent, q represents an integer from 1
to 4, and
the alkylene group has from one to four carbon atoms, A (alkylene)q for
example
being N(CH2CH2)3; C(CH2)4; or (CH2)2; and R25 may independently be
s (a) n-alkyl-
(b) n-alkyl-CO-
(c) n-alkyl-OCO-(CH2)~-
(d) n-alkyl-OCO-(CH2)~CO-
~o n being, for example, 1 to 34, the alkyl group being linear and containing
from 10 to
30 carbon atoms. For example, they may be represented by the formula
R230BOR2a,
R23 and R24 each being defined as for R25 above, and B representing the
polyalkylene segment of the glycol in which the alkylene group has from 1 to 4
carbon atoms, for example, polyoxymethylene, polyoxyethylene or
is polyoxytrimethylene moiety which is substantially linear; some degree of
branching
with lower alkyl side chains (such as in polyoxypropylene glycol) may be
tolerated but
it is preferred that the glycol should be substantially linear.
(iii) The non-ethylene hydrocarbon polymer may be an oil-soluble hydrogenated
2o block diene polymer, comprising at least one crystallizable block,
obtainable by end-
to-end polymerisation of a linear diene, and at least one non-crystallizable
block, the
non-crystallizable block being obtainable by 1,2-configuration polymerisation
of a
linear diene, by polymerisation of a branched diene, or by a mixture of such
polymerisations.
2s
Advantageously, the block copolymer before hydrogenation comprises units
derived
from butadiene only, or from butadiene and at least one comonomer of the
formula
CH2 = CR4° - CR4' = CH2
wherein R4° represents a C~ to C8 alkyl group and R4' represents
hydrogen or a C~ to
C8 alkyl group. Advantageously the total number of carbon atoms in the
comonomer
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
28
is 5 to 8, and the comonomer is advantageously isoprene. Advantageously, the
copolymer contains at least 10% by weight of units derived from butadiene.
(iv) These materials are condensates comprising aromatic and hydrocarbyl
parts.
s The aromatic part is conveniently an aromatic hydrocarbon which may be
unsubstituted or substituted with, for example, non-hydrocarbon substituents.
Such aromatic hydrocarbon preferably contains a maximum of three substituent
groups and/or three condensed rings, and is preferably naphthalene. The
to hydrocarbyl part is a hydrogen and carbon containing part connected to the
rest of
the molecule by a carbon atom. It may be saturated or unsaturated, and
straight or
branched, and may contain one or more hetero-atoms provided they do not
substantially affect the hydrocarbyl nature of the part. Preferably the
hydrocarbyl part
is an alkyl part, conveniently having more than 8 carbon atoms.
In addition, the additive composition may comprise one or more other
conventional
co-additives known in the art, such as detergents, antioxidants, corrosion
inhibitors,
dehazers, demulsifiers, metal deactivators, antifoaming agents, cetane
improvers,
cosolvents, package compatibifities, and lubricity additives and antistatic
additives.
The co-additives may be added to the additive composition at the same time as
any
of the additives (I), (II) and if appropriate (III) or at different times.
The fuel oil composition, additive composition, or additive concentrate of the
fifth to
2s seventh aspects may additionally comprise one or more co-additives useful
in fuel oil
compositions. Such co-additives include, for example, oxygenates, such as t-
butyl
methyl either, anntiknock agents, such as methylcyclopentadienyl manganese
tricarbonly, lead scavengers such as aryl or alkyl halides, and detergents,
such as
alkali or alkaline earth metal salt, polyalkenyl amines, e.g.
polybutyleneamines, such
3o as "KEROCOM" polyisobutyleneamine, available ex BASF, Mannich amines,
polyalkenyl succinimides, poly(oxyalkylene)amines, poly(oxyalkylene)
carbamates,
poly(alkenyl)-N-substituted carbamates, and mixtures thereof, and dispersants.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
29
Additionally, antioxidants, such as phenolics, e.g. 2,6-di-tert-butylphenol or
phenylenediamines, e.g. N,N'-di-sec-butyl-p-phenylenediamine, metal
deactivators,
demulsifiers and carburetor or fuel injector detergents may be present.
Corrosion
inhibitors, such as that commercially sold by Rhein Chemie, Mannheim, Germany
as
s "RC 4801", or a polyhydric alcohol ester of a succinic acid derivative
having on at
least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic
hydrocarbon group having from 20 to 500 carbon atoms, for example,
pentaerythritol
diester of polyisobutylene-substituted succinic acid, the polyisobutylene
group having
an average molecular weight of about 950, in an amount from about 1 ppmw to
about
~0 1000 ppmw, may also be present.
Other Aspects Of the Invention
The invention further provides a process for the manufacture of the fuel oil
~s composition of the first aspect or fourth or fifth aspect, comprising:
(i) obtaining the desired fuel oil, and
(ii) blending therewith the additive composition, or additive concentrate, or
additives , for example, (I), (II), and optionally (III) of the present
invention.
2o The invention also provides a method of operating an oil refinery or fuel
oil
manufacturing facility comprising:
(i) manufacturing a fuel oil with low temperature properties insufficient to
meet
the required technical specification for that oil,
2s
(ii) improving such properties through the addition thereto of the additive
composition, or additive concentrate, or the additives (I), (II), and
optionallly
(III) of the present invention in an amount sufficient to meet the required
specification.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
The additive (I) shows excellent physical compatibility with co-additives ,
for example
(II) and (III), and provides enhanced lubricity performance at lower treat
rates of
additive (I) in combination with additives, for example (II) and (III).
s An advantage of the invention is that a substantial portion of the aromatic
condensate
can be replaced by additive (I) in fuel oil compositions which also comprise
additive
(III) whilst still maintaining or improving the low temperature properties,
for example
CFPP, and sustaining the wax antisettling performance in fuel oils.
~o Another aspect of the present invention is the use of (I) and (II) and
optionally (III) as
defined under the first aspect, or the additive composition of the second
aspect, or
the concentrate of the third aspect, in a fuel oil to improve the lubricity of
the fuel oil.
Further the present invention provides the use of (I), (II) and (III) as
defined under the
~s first aspect, or the additive composition or additive concentrate of the
second and
third aspect respectively, each of which comprises, or is obtainable by
admixing, (I),
(II) and (III) as defined under the first aspect, in a fuel oil to improve the
low
temperature flow properties of the fuel oil, particularly low temperature
filterability.
2o An advantage of the present invention is that additive (I) may be used at
reduced
treat-rates in fuel oil compositions, which can also contain (II) and
optionally (III),
particularly in order to enhance lubricity performance.
Another advantage is that additive (I) may be used to replace a substantial
portion of
2s aromatic condensate in fuel oil compositions, which also contain (III),
whilst
maintaining or even improving the low temperature properties, for example
CFPP.
In the process, method, use and other aspects of the invention, the preferred
embodiments of (I), (II) and (III) are those as described under the fuel oil
composition
3o aspect of the invention.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
31
Further with respect to the fifth to eighth aspects of the present invention,
use of
additive (I) in combination with a co-additive such as a detergent in a
gasoline fuel
composition surprisingly results in reduced undesirable effects, for example
reduced
inlet valve deposits, compared to other lubricity addtives.
Treat-Rates
Preferably the amount of additive (I) in the fuel oil composition is in the
range of from
5 to 500 ppm (active ingredient or a.i) by mass based on the mass of the
to composition; such as 5 to 250 or 5 to 150; especially 5 to 50; more
preferably 10 to
40 ppm by mass; such as 10 to 30 ppm by mass.
Preferably the amount of aromatic condensate in the fuel oil composition is
not more
than 150 ppm (active ingredient or a.i) by mass based on the mass of the
is composition; more preferably less than 100 ppm by mass; such as less than
75 ppm
by mass; especially in the range of from 10 to 50 ppm by mass.
Preferably the amount of ethylene polymer in the fuel oil composition is not
more
than 500 ppm (active ingredient or a.i) by mass based on the mass of the
2o composition; more preferably less than 250 ppm by mass, such as 150 ppm by
mass;
especially in the range of from 50 to 125 ppm by mass.
Preferably the amount of additive (III) in the fuel oil composition is not
more than 200
ppm (active ingredient or a.i) by mass based on the mass of the composition;
more
2s preferably less than 150 ppm by mass; such as in the range of from 50 to
125 ppm
by mass.
The effective amount of the combination of (I), (II), and optionally (III) in
the fuel oil
composition may for example be in the range of 1 to 5,000 ppm (active
ingredient) by
3o mass based on the mass of the composition, for example 10 to 5,000 ppm such
as
25 to 2500 ppm (active ingredient), preferably 50 to 1000 ppm, more preferably
100
to 800 ppm.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
32
Where co-additives are also present, the amount of the additive composition
may be
correspondingly higher, for example 10 to 10,000 ppm (active ingredient) such
as 50
to 5,000 ppm, more preferably 100 to 2,500 ppm.
s
Preferably the ratio of (1):(11):(111) is in the range of from 1 - 50 mass%:
20 - 90 mass
%: 0 - 60 mass %; more preferably 2 - 40 mass%: 20 - 80 mass %: 5 - 60 mass
%; especially 2 - 30 mass %: 30 - 70 mass %: 10 - 50 mass %.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPOI/04177
33
The invention will now be described further by reference to the examples only
as
follows:
Examples
s The following materials and procedures were used.
Additive A: 2-hydroxyethyl salicylate
Additive B: mixture of ethylene vinyl acetate growth arrestor and ethylene
vinyl
acetate nucleator in 3:1 ratio by mass
to Additive C: Nonylphenol-formaldehyde condensate
Additive D: amide - amine salt formed by reacting 1 molar portion of phthalic
anhydride with 2 molar proportions of dihydrogenated tallow amine
Fuel oils
Fuel1 Fuel2 Fuel3 Fuel4
CFPP Fail temperature-29C -36C -9C -11 C
Density 0.8215g/10.8148g/10.8357 0.8302
D86 Distillation
(C)
I B P 190.2 192.9 173.1 174
D5% 209.3 203.5 198.2 191
D10% 212.9 208.3 201.7 194
D20% 223.0 215.7 215.8 203
D30% 230.2 222.8 227 213
D40% 237.3 231.0 239.1 224
D50% 244.8 238.7 252 237
D60% 252.3 245.9 265.8 254
D70% 260.9 253.5 280.9 272
D80% 271.7 262.3 299.9 295
D90% 285.8 274.8 324.6 323
D95% 297.1 286.1 344.1 342
FBP 307.2 291.2 354.2 354
Flash Point 74.5 C 73.5
C
Pour Point i -24C -33C
Sulphur content <100 ppm <100
ppm
KV20C ~ 3.092 2.996
cSt cSt
KV40C 2.035 2.133
cSt cSt
Fuel oil compositions were prepared in the proportions shown in the Examples
and
the resulting fuel oil compositions were tested in the High Frequency
Reciprocating
Rig Test (or "HFRR") for lubricity performance. The HFRR test method is
described
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
34
in the industry standard test methods CEC PF 06-T-94 and
ISO/TC22/SC7/WG6/W188 and was performed at 60°C. Selected fuel oil
compositions were also tested to evaluate their ability to improve the low
temperature
properties of a fuel, as measured by their CFPPs, as described in European
s Standard method EN116.
Comparative Example 1
Fuel oil compositions were prepared in the proportions shown below in Fuel 1
and
tested in the HFRR.
to
Treat HFRR (~)
rate
(ppm
ai)
AdditiveAdditiveAdditive AdditiveTotal
A B C D
0 - - - 0 656
25 - - - 25 538
50 - - - 50 543
75 - - - 75 533
100 - - - 100 426
150 - - - 150 400
200 - - - 200 337
- 150 - - 150 636
- 200 - - 200 626
- - 150 - 150 644
- - 200 - 200 574
- - 62.5 62.5 125 602
- - 75 75 150 535
- - 100 100 200 411
Example 1
is Fuel oil compositions were prepared in the proportions shown below in Fuel
1 and
tested in the HFRR.
Treat rate HFRR (p)
(ppm ai)
Additive A Additive B Total
37.5 112.5 150 577
50 150 200 ~ 317
The data clearly show that the HFRR performance is improved as the total treat
rate
20 of Additive A and Additive B is increased from 150 to 200ppm. Further, the
Applicant
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
was surprised to find that good HFRR performance is achieved at treat rates as
low
as 50 ppm of Additive A in combination with Additive B (see Comparative
Example
1 ).
s Example 2
Fuel oil compositions were prepared in the proportions shown below in Fuel 1
and
tested in the HFRR.
Treat HFRR (~)
rate
(ppm
ai)
Additive Additive C Additive Total
A D
38 113 - 150 369
50 150 - 200 303
19 56 75 150 350
25 75 100 200 313
30 ~ 45 4S 120 313
Similar to Example 1, the data clearly show an improvement in the HFRR
performance for compositions containing both Additive A and C, in particular
at low
low treat rates of Additive A (see Comparative Example 1 ). This trend is also
observed for compositions containing Additive A, C and D.
Is
Example 3
Fuel oil compositions were prepared in the proportions shown below in Fuel 1
and
tested in the HFRR.
Treat HFRR (~)~
rate
(ppm
ai)
Additive Additive Additive Additive Total
A B C D
16 100 47 63 225 266
- 100 47 63 210 585
- 100 63 63 226 466
20 - 94 - 114 534
20 100 94 - 214 384
average of .s measurements
Compositions containing Additives A, B, and C demonstrated enhanced HFRR
performance compared to compositions containing only Additives A and C. This
is
particularly significant at lower treat rates of Additive A (see Example 2).
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
36
Example 4
Fuel oil compositions were prepared in the proportions shown below in Fuel 3
and
tested in the HFRR and their CFPP measured. Each composition also contained
Additive B at 100 ppm (active ingredient) for CFPP measurements.
Treat rate CFPP (C) HFRR (~)
(ppm ai)
Additive Additive Additive
A C D
- - 100 -27 -
- 50 50 -27 455
20 35 45 -28 245
Example 5
Fuel oil compositions were prepared in the proportions shown below in Fuel 4
and
tested in the HFRR and their CFPP measured. Each composition also contained an
~o ethylene vinyl acetate growth arrestor (28 wt % vinyl acetate and 72 wt %
ethylene;
having a number average molecular weight of 3200) at 100 ppm (active
ingredient)
for CFPP measurements.
Treat rate CFPP (C) HFRR (u)
(ppm ai)
Additive Additive Additive
A C D
- 100 -25 -
50 50 -21 562
20 35 45 -27 280
~s The data in Examples 4 and 5 clearly show an improvement in the HFRR
performance at low treat rates of Additive A whilst maintaining, or even
improving, the
CFPP performance.
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
37
Example 6
Fuel oils
Fuel5 Fuel6
Density @ 15C (g/L) 0.7393 0.7491
RON (research octane number)96.8 95.5
MON (motor octane number) 85 84.8
Distillation
IBP 26.9 29.5
10% 43.3 48
20% 51.4 59.5
30% 60.3 71.5
40% 71.2 84.5
50% 84.5 97.5
60% 102.1 110.5
70% 119.1 124.0
80% 130.8 139.0
90% 150.7 158.0
95% 168.2 170.0
FBP 199.7 196.5
Sulfur (mass %) 0.013 0.0165
Additives
Additive E: a PIB amine detergent (1300 Mw PIB)
Additive F: a PIB amine detergent (950 Mw PIB)
Additive G: glycerol mono- and di-esters of unsaturated fatty acids (a
lubricity
additive)
~o Additive H: ethoxylated C36 dimer acid (a lubricity additive)
CA 02403793 2002-09-19
WO 01/79397 PCT/EPOI/04177
38
Gasoline fuel oil compositions were prepared in the proportions shown below
and the
resulting fuel oil compositions were tested in Mercedes-Benz M102 E test
according
to procedure CEC F-05-A-93.
Additive fuel
Treat
rate
(ppm
ai)
E F A G H
Example 6a 480 - - - - 5
(comparative)
Example 6b 480 - 100 - 5
(comparative)
Example 6c 480 - - - 100 5
(comparative)
Example 6d - - - - - 6
(comparative)~
Example 6e - 581 - - - 6
(comparative)
Example 6f - 670 - - - 6
(comparative)
example S I _ I 670 ~ 100 I - I __ I 6
"Example 6d is base fuel
CA 02403793 2002-09-19
WO 01/79397 PCT/EPO1/04177
39
Briefly, the M102E test evaluates the effect of gasoline fuel compositions on
the
formation of inlet valve deposits, in passenger car engines with fuel
injection. This
test allows the effectiveness of different fuel additives to be evaluated.
Results of M102E Test
Inlet CCD* Valve
Valve (g/cylinder)rating
Desposits
(mg/valve)
V1 V2 V3 V4 Ave. Ave. Ave.
Example 6a 49 61 167 185 116 1.9313 9.1
Example 6b 597 617 591 728 633 1.739 7.2
Example 6C 845 1200 1194 1340 1145 1.919 6.1
Example 6d 340 232 354 388 329 1.520 7.8
Example se 44 58 125 53 70 2.134 9.4
Example 6f 27 48 9 4 22 2.235 9.8
Example 6 34 246 47 101 107 1.987 9.1
"' combustion chamber deposits
The results show that when a detergent additive is present, then good
performance
us observed (see Examples 6a & 6d to 6f). However, on addition of certain
lubricity
to additives, for example additives G and H to the fuel composition, which
also has a
detergent, the inlet valve deposits are substantially increased (see Examples
6a-6c).
In contrast and surprisingly, the use of additive A, an example of additive
(I)
according to the invention, results in minimising the increase in inlet valve
deposits
is (see Example 6 compared to Examples 6d to 6f)).
