U.S. patent application number 13/482773 was filed with the patent office on 2012-12-06 for liquid fuel compositions.
This patent application is currently assigned to SHELL OIL COMPANY. Invention is credited to Mark Lawrence Brewer, Susan Jane Smith.
Application Number | 20120304531 13/482773 |
Document ID | / |
Family ID | 44303281 |
Filed Date | 2012-12-06 |
United States Patent
Application |
20120304531 |
Kind Code |
A1 |
Brewer; Mark Lawrence ; et
al. |
December 6, 2012 |
LIQUID FUEL COMPOSITIONS
Abstract
A liquid fuel composition is provided containing: (a) a base
fuel suitable for use in an internal combustion engine; (b) a first
fuel additive selected from one or more viscosity control agents
having: (i) a kinematic viscosity at 100.degree. C. of 27 cSt or
less; and (ii) a NOACK volatility at 250.degree. C. of 100% wt or
less; and (c) a second fuel additive selected from one or more
friction modifiers. Fuelling such liquid fuel composition in an
internal combustion engine improves the fuel economy performance of
an internal combustion engine.
Inventors: |
Brewer; Mark Lawrence;
(Chester, GB) ; Smith; Susan Jane; (Chester,
GB) |
Assignee: |
SHELL OIL COMPANY
Houston
TX
|
Family ID: |
44303281 |
Appl. No.: |
13/482773 |
Filed: |
May 29, 2012 |
Current U.S.
Class: |
44/347 ; 44/385;
44/386; 44/401; 44/434; 44/451 |
Current CPC
Class: |
C10L 1/14 20130101; C10L
1/19 20130101; C10L 1/2387 20130101; C10L 1/1641 20130101; C10L
1/1883 20130101; C10L 1/1985 20130101; C10L 1/224 20130101; C10L
1/191 20130101; C10L 1/1826 20130101; F02B 47/04 20130101 |
Class at
Publication: |
44/347 ; 44/385;
44/386; 44/401; 44/434; 44/451 |
International
Class: |
C10L 1/232 20060101
C10L001/232; C10L 1/182 20060101 C10L001/182; C10L 1/224 20060101
C10L001/224; C10L 1/188 20060101 C10L001/188; C10L 1/19 20060101
C10L001/19 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2011 |
EP |
11168052.6 |
Claims
1. A liquid fuel composition comprising: (a) a base fuel suitable
for use in an internal combustion engine; (b) a first fuel additive
selected from one or more viscosity control agents having: (i) a
kinematic viscosity at 100.degree. C. of 27 cSt or less; and (ii) a
NOACK volatility at 250.degree. C. of 100% wt or less; and (c) a
second fuel additive selected from one or more friction
modifiers.
2. The liquid fuel composition of claim 1 wherein the one or more
friction modifiers is selected from the group consisting of esters
or nitrogen derivatives of alkoxyamines; poly(hydroxycarboxylic)
acid amide salt derivatives; poly(hydroxycarboxylic acid)
derivatives having a terminal acid group; poly(hydroxycarboxylic
acid) derivatives; polyetheramines; esters or nitrogen derivatives
of hydroxy polycarboxylic acids; nitrogen derivatives of carboxylic
acids; ester derivatives of carboxylic acids; esters of
alkylsuccinic acids; alkoxylated alcohols; alkoxylated amines;
alkoxylated amides or esters; and mixtures thereof.
3. The liquid fuel composition of claim 2 wherein the one or more
friction modifiers is selected from the group consisting of
poly(hydroxycarboxylic) acid amide salt derivatives;
poly(hydroxycarboxylic acid) derivatives having a terminal acid
group; poly(hydroxycarboxylic acid) derivatives; polyetheramines;
ester or nitrogen derivatives of alkoxyamines; alkoxylated amides
or esters; alkoxylated amines; and mixtures thereof.
4. The liquid fuel composition of claim 1 wherein the amount of the
second fuel additive present in the liquid fuel composition is at
least 10 ppmw, based on the overall weight of the liquid fuel
composition.
5. The liquid fuel composition of claim 4 wherein the amount of the
second fuel additive present in the liquid fuel composition is at
most 2 wt %, based on the overall weight of the liquid fuel
composition.
6. The liquid fuel composition of claim 1 wherein the first fuel
additive has a NOACK volatility at 250.degree. C. of 20% wt or
less.
7. The liquid fuel composition of claim 1 wherein the first fuel
additive has a NOACK volatility at 250.degree. C. of 15% wt or
less.
8. The liquid fuel composition of claim 1 wherein the first fuel
additive has a NOACK volatility at 250.degree. C. of 10% wt or
less.
9. The liquid fuel composition of claim 1 wherein the first fuel
additive has a NOACK volatility at 250.degree. C. of 6% wt or
less.
10. The liquid fuel composition of claim 1 wherein the first fuel
additive has a kinematic viscosity at 100.degree. C. of 17 cSt or
less.
11. The liquid fuel composition of claim 1 wherein the first fuel
additive has a kinematic viscosity at 100.degree. C. in the range
of from 2 cSt to 8 cSt.
12. The liquid fuel composition of claim 1 wherein the first fuel
additive has a kinematic viscosity at 100.degree. C. in the range
of from 3 cSt to 8 cSt.
13. The liquid fuel composition of claim 1 wherein the first fuel
additive has a kinematic viscosity at 100.degree. C. in the range
of from 4 cSt to 6 cSt.
14. The liquid fuel composition of claim 1 wherein the first fuel
additive is a polyalphaolefin.
15. The liquid fuel composition of claim 9 wherein the first fuel
additive is PAO-5.
16. The liquid fuel composition of claim 1 wherein the first fuel
additive is an ester.
17. The liquid fuel composition of claim 16 wherein the first fuel
additive is a trimethyl propane ester.
18. The liquid fuel composition of claim 1 wherein the amount of
first fuel additive present in the liquid fuel composition is in
the range of from 5 ppmw to 2% wt, based on weight of the liquid
fuel composition.
19. The liquid fuel composition of claim 1 wherein the base fuel is
a gasoline.
20. A method of improving the fuel economy performance of an
internal combustion engine, said method comprising (a) fuelling the
internal combustion engine containing a lubricant with a liquid
fuel composition of claim 1 and (b) operating said fuelled-internal
combustion engine.
Description
[0001] The present application claims the benefit of pending
European Patent Application No. 11168052.6, filed May 30, 2011 the
entire disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a liquid fuel
composition.
BACKGROUND OF THE INVENTION
[0003] Government regulations and market demands continue to
emphasize conservation of fossil fuels in the transportation
industry. There is increasing demand for more fuel-efficient
vehicles in order to meet CO.sub.2 emissions reductions targets.
Therefore, any incremental improvement in fuel economy (FE) is of
great importance in the automotive sector. Lubricants can play an
important role in reducing a vehicle's fuel consumption and there
is a continuing need for improvements in fuel economy performance
of lubricant compositions contained within an internal combustion
engine.
[0004] R. I. Taylor & R. C. Coy, "Improved Fuel Efficiency by
Lubricant Design: A Review", Proc Instn Mech Engrs, Vol 214, Part
J, pp 1-15, 2000, reviews the properties of the lubricant
composition that affect fuel consumption. In particular, this
review paper teaches that one of the properties of a lubricant
composition which affects the fuel economy performance of that
lubricant composition is viscosity. The lower the viscosity of the
lubricant composition, the greater the fuel economy performance of
that lubricant composition [SAE 982502]. However, viscosity
increase is often observed during an oil drain interval (ODI) [SAE
2008-01-1740], which is expected to be detrimental to fuel
economy.
SUMMARY OF THE INVENTION
[0005] Accordingly, in one embodiment provides a liquid fuel
composition comprising: [0006] (a) a base fuel suitable for use in
an internal combustion engine; [0007] (b) a first fuel additive
selected from one or more viscosity control agents having: [0008]
(i) a kinematic viscosity at 100.degree. C. of 27 cSt or less; and
[0009] (ii) a NOACK volatility at 250.degree. C. of 100% wt,
preferably 20% wt or less; and [0010] (c) a second fuel additive
selected from one or more friction modifiers.
[0011] In a further embodiment provides a method of improving the
fuel economy performance of an internal combustion engine, said
method comprising (a) fuelling an internal combustion engine
containing an engine lubricant with such liquid fuel composition
and (b) operating said fuelled-internal combustion engine.
DETAILED DESCRIPTION OF THE INVENTION
[0012] While the lubricant formulation remains fixed from the
beginning, an opportunity has been identified to influence the
lubricant positively via the fuel composition, in particular by
adding certain fuel additives to the fuel composition.
[0013] Viscosity control additives such as polyalphaolefins and
esters are known for use in liquid fuel compositions and have been
disclosed in the following patent publications: EP-A-707058;
EP-A-290088; EP-A-634472; WO98/11178 and WO98/11177.
[0014] EP-A-707058 and discloses a fuel composition comprising a
gasoline base fuel, a polyalphaolefin and a detergent which may be
a polyisobutylenyl succinimide or an aliphatic or alkoxylated
polyamine. EP-A-634472 also discloses a fuel composition comprising
a gasoline base fuel, a polyalphaolefin and a succinimide. A
detergent in a fuel composition aids performance by cleaning the
internal parts of an engine during use and reducing engine
deposits. Detergents in general, and succinimide derivatives in
particular, do not contribute significantly to lubricity and
reduced friction, and are not therefore known to act as friction
modifiers, nor to aid fuel economy via friction reduction.
[0015] It has now been found that the use of selected viscosity
control additives having certain physical properties together with
selected friction modifiers in liquid fuel compositions can provide
benefits in terms of improved fuel economy and improved engine
lubricant performance.
[0016] The liquid fuel composition contains a base fuel suitable
for use in an internal combustion engine, a first fuel additive
selected from viscosity control agents having certain physical
properties and a second fuel additive which is a friction modifier.
Typically, the base fuel suitable for use in an internal combustion
engine is a gasoline or a diesel fuel, and therefore the liquid
fuel composition of the present invention is typically a gasoline
composition or a diesel fuel composition.
[0017] As used herein, the term "viscosity control additive" or
"VCA" is a fuel-borne additive intended to control increases in
lubricant viscosity. As used herein, the term "friction modifier"
or "FM" is an additive intended to reduce the coefficient of
friction, normally in the boundary lubrication regime.
[0018] The first fuel additive used in the liquid fuel composition
herein is a viscosity control agent (VCA) and has a kinematic
viscosity at 100.degree. C. (as measured by ASTM D 445 or IP71) of
27 cSt or less. Preferably, the kinematic viscosity at 100.degree.
C. (as measured by ASTM D 445) additionally accords with one or
more of the parameters listed below: [0019] (i) 22 cSt or less;
[0020] (ii) 17 cSt or less; [0021] (iii) 13 cSt or less; [0022]
(iv) 10 cSt or less; [0023] (v) 8 cSt or less; [0024] (vi) 6 cSt or
less; [0025] (vii) 5.5 .cSt or less; [0026] (viii) At least 2 cSt;
[0027] (ix) At least 3 cSt; [0028] (x) At least 3.5 cSt; [0029]
(xi) At least 4 cSt; [0030] (xii) At least 4.5 cSt.
[0031] In preferred embodiments herein the first fuel additive has
a kinematic viscosity at 100.degree. C. (as measured by ASTM D 445)
in the range of from 2 cSt to 8 cSt, preferably in the range of
from 3 cSt to 8 cSt, more preferably in the range of from 3.5 cSt
to 6 cSt, even more preferably in the range of from 4 cSt to 6 cSt,
especially in the range of from 4 cSt to 5.5 cSt, more especially
in the range of from 4.5 cSt to 5.5 cSt.
[0032] In addition, the first fuel additive used in the liquid fuel
composition herein has a NOACK volatility (as measured by ASTM
D5800 at 250.degree. C.) of 100 wt % or less, preferably 20 wt % or
less, preferably 10 wt % or less, more preferably 6 wt % or less,
even more preferably 5 wt % or less, especially 4 wt % or less.
[0033] Suitable viscosity control agents for use as the first fuel
additive herein include polyalphaolefins, esters, alkyl benzenes
and alkyl naphthenates. Other suitable viscosity control agents for
use herein include other base lubricant oils provided they have the
required kinematic viscosity and NOACK volatility. Other suitable
base lubricant oils can be found in "Synthetic Lubricants and High
Performance Function Fluids", 1999, 2.sup.nd Edition, edited by L R
Rudnick. The viscosity control agents can be used individually or
as mixtures of two or more VCAs.
[0034] Poly-alpha olefin base oils (PAOs) and their manufacture are
well known in the art. Preferred poly-alpha olefin base oils that
may be used in the fuel compositions of the present invention may
be derived from linear C.sub.2 to C.sub.32, preferably C.sub.6 to
C.sub.16, alpha olefins. Particularly preferred feedstocks for said
poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and
1-tetradecene. Poly-alpha olefins can be prepared from single
component streams or mixed component streams.
[0035] Suitable polyalphaolefins for use herein include PAO-5,
PAO-2, PAO-4, PAO-6 and PAO-8, preferably PAO-5.
[0036] Commercially available polyalphaolefins for use herein
include those available from Ineos under the tradenames Durasyn
125, Durasyn 126, Durasyn 127, Durasyn 128, Durasyn 145, Durasyn
147, Durasyn 148, Durasyn 156, Durasyn 162, Durasyn 164, Durasyn
165, Durasyn 166, Durasyn 168, Durasyn 170 and Durasyn 174; those
available from Exxon Mobil Corporation under the tradename
Spectrasyn 4, Spectrasyn 5, Spectrasyn 6, Spectrasyn 8 and
Spectrasyn 10; those available from Chevron Corporation under the
tradenames Synfluid PAO 2, Synfluid PAO 4, Synfluid PAO 5, Synfluid
PAO 6, Synfluid PAO 7, Synfluid PAO 8 and Synfluid PAO 9; and those
commercially available from Neste under the tradenames Nexbase
2002, Nexbase 2004, Nexbase 2006 and Nexbase 2008.
[0037] Ester compounds for use herein may be used alone or as
mixtures of one or more esters. Preferably the ester compounds for
use herein have a molecular weight of 200 or greater, or has at
least 10 carbon atoms, or has both.
[0038] Examples of esters that may be used are lower alkyl esters,
such as methyl esters, of saturated or unsaturated monocarboxylic
acids. Such esters may, for example, be obtained by saponification
and esterification of natural fats and oils of plant or animal
origin or by their transesterification with lower aliphatic
alcohols.
[0039] Suitable acids from which the esters are derived include
mono or polycarboxylic acids such as aliphatic, saturated or
unsaturated, straight or branched chain, mono and dicarboxylic
acids being preferred. For example, the acid may be generalised by
the formula R'(COOH).sub.x where x represents an integer and is 1
or more such as 1, 2, 3 or 4, and R' represents a hydrocarbyl group
having from 2 to 50 carbon atoms and which is mono or polyvalent
corresponding to the value of x, the --COOH groups, when more than
one is present, optionally being substituent on different carbon
atoms from one another.
[0040] As used in the context of the acids from which the esters
are derived the term `Hydrocarbyl` means a group containing carbon
and hydrogen which group is connected to the rest of the molecule
via a carbon atom. It may be straight or branched chain which chain
may be interrupted by one or more hetero atoms such as O, S, N or
P, may be saturated or unsaturated, may be aliphatic or alicyclic
or aromatic including heterocyclic, or may be substituted or
unsubstituted. Preferably, when the acid is monocarboxylic, the
hydrocarbyl group is an alkyl group or an alkenyl group having 6
(e.g. 12) to 30 carbon atoms, i.e. the acid is saturated or
unsaturated. The alkenyl group may have one or more double bonds,
such as 1, 2 or 3. Examples of saturated carboxylic acids are those
with 6 to 22 carbon atoms such as caproic, caprylic, capric,
lauric, myristic, palmitic, and behenic acids and examples of
unsaturated carboxylic acids are those with 10 to 22 carbon atoms
such as oleic, elaidic, palmitoleic, petroselic, ricinoleic,
eleostearic, linoleic, linolenic, eicosanoic, galoleic, erucic and
hypogeic acids. When the acid is polycarboxylic, having for example
from 2 to 4 carboxy groups, the hydrocarbyl group is preferably a
substituted or unsubstituted polymethylene. Examples of
polycarboxylic acids include adipic acid, sebacic acid, azelaic
acid, phthalic acid, fumaric acid and dimer acids or di-linoleic
acid commercially available as Unidyme 22 from Arizona
Chemical.
[0041] The alcohol from which the ester is derived may be a mono or
polyhydroxy alcohol such as a trihydroxy or tetrahydroxy alcohol.
For example, the alcohol may be generalised by the formula
R.sup.2(OH).sub.y where y represents an integer and is 1 or more
and R.sup.2 represents a hydrocarbyl group having 1 or more carbon
atoms such as up to 10 carbon atoms, and which is mono or
polyvalent corresponding to the value of y, the --OH groups, when
more than one is present, optionally being substituent on different
carbon atoms from one another.
[0042] The term `Hydrocarbyl` in the context of the alcohol has the
same meaning as given above for the acid. For the alcohol, the
hydrocarbyl group is preferably an alkyl group or a substituted or
unsubstituted polymethylene group. Examples of monohydric alcohols
are lower alkyl alcohols in which the alkyl group may be straight
chain or branched having from 1 to 8 carbon atoms such as methyl,
ethyl, propyl, butyl, pentyl, octyl and 2-ethylhexyl alcohols.
[0043] Examples of polyhydric alcohols are aliphatic, saturated or
unsaturated, straight chain or branched alcohols having 2 to 10,
preferably 2 to 6, more preferably 2 to 4, hydroxy groups, and
having 2 to 90, preferably 2 to 30, more preferably 2 to 12, most
preferably 2 to 6, carbon atoms in the molecule. As more particular
examples the polyhydric alcohol may be a glycol or diol such as
neopentylglycol (NPG), or a trihydric alcohol such as glycerol or
trimethylolpropane (TMP) or tetrahydric alcohol such as
pentaerythritol (PE). Examples of esters of polyhydric alcohols
that may be used are those where all of the hydroxy groups are
esterified, those where not all of the hydroxy groups are
esterified, i.e. the ester may have one or more free hydroxy
groups, and mixtures thereof. Preferably all of the hydroxy groups
are esterified. Specific examples are esters prepared from
trihydric alcohols and one or more of the above-mentioned saturated
or unsaturated carboxylic acids, such as TMP monoesters, TMP
diesters, and TMP triesters e.g. TMP monooleate, TMP dioleate, TMP
tricaproate, glycerol monooleate, glycerol dioleate and glycerol
tricaproate. The alcohols may be esterified with two or more
different acids. Such polyhydric esters may be prepared by
esterification as described in the art and/or may be commercially
available.
[0044] Examples of suitable esters for use herein include the
dimerate esters commercially available under the tradenames
Priolube 1858, Priolube 3967, Emkarate 1220, Emkarate 9200,
Emkarate 1120 and Emkarate 1090 from Croda Europe, Palatinol 9P
from BASF and Hatcol 2949 from Chemtura, Uniflex 102e from Arizona
Chemical; monoesters commercially available under the tradename
Synative ES EHO from Cognis (now BASF), pentaerythritol esters
commercially available under the tradenames Priolube 1445 and
Priolube 3987 from Croda Europe; trimellitate esters commercially
available under the tradenames Emkarate 7930, Emkarate 3030,
Emkarate 1030, Emkarate 8030 and Priolube 1941 from Croda Europe;
trimethylolpropane esters commercially available under the
tradenames Priolube 1427, Priolube 3970 and Priolube 3988 from
Croda Europe, Synative ES TMP 05 from Cognis GmbH and Radialube
7364, Radialube 7365 and Radialube 3988 from Oleon; and polyol
esters commercially available under the tradenames Priolube 1426,
Priolube 1973 from Croda Europe, Radialube 7304 from Oleon nv, and
EsterexNP343, EsterexNP372, EsterexNP451, EsterexNP671 and
EsterexNP396 from Exxon Mobil Corporation.
[0045] Preferred ester compounds for use herein include esters of
neopentylglycol (NPG), trimethylolpropane, or pentaerythritol. A
particularly preferred ester compound for use herein is a C7-C9
ester of trimethylolpropane commercially available under the
tradename Priolube 3970 from Croda Europe Limited. Another
particular preferred ester compound for use herein is a
cocoate/C8-C10 ester of neopentylglycol commercially available
under the tradename Synative ES 3824 from Cognis (now BASF) or
Nycobase 8210 from Nyco.
[0046] Another particularly preferred ester for use herein is the
diester diisodecylazelate such as Priolube 1858 commercially
available from Croda.
[0047] Another particular preferred ester for use herein is the
monoester 2-ethylhexyl oleate commercially available under the
tradename Synative ES EHO from Cognis (now BASF).
[0048] Alkyl naphthenates and their preparation are known in the
art. Suitable alkyl-substituted naphthalenes include
alpha-methylnaphthalene, dimethylnaphthalene and ethylnaphthalene.
Suitable alkyl naphthenates for use herein and their preparation
methods include, but are not necessarily limited to, those
disclosed in US2004/0018944, WO02/04578, U.S. Pat. No. 5,502,086
and EP-A-0,496,486. Examples of commercially available alkyl
naphthenates include those from Exxon Mobil Corporation under the
tradenames Synesstic 5 and Synesstic 12, and those from King
Industries, Inc. under the tradenames NA-LUBE KR008 and NA-LUBE
KR019.
[0049] Alkyl benzenes and their preparation are known in the art.
Suitable alkyl benzenes for use herein include, but are not
necessarily limited to, those disclosed in WO02/04578, U.S. Pat.
No. 5,502,086 and EP-A-0,496,486.
[0050] Preferably, the amount of the first fuel additive having a
viscosity of less than 27 cSt and a NOACK volatility of 100% wt or
less, preferably 20% wt or less, present in the liquid fuel
composition of the present invention is at least 5 ppmw (parts per
million by weight), based on the overall weight of the liquid fuel
composition. More preferably, the amount of first fuel additive
present in the liquid fuel composition of the present invention
additionally accords with one or more of the parameters (i) to (xx)
listed below: [0051] (i) at least 10 ppmw [0052] (ii) at least 20
ppmw [0053] (iii) at least 30 ppmw [0054] (iv) at least 40 ppmw
[0055] (v) at least 50 ppmw [0056] (vi) at least 100 ppmw [0057]
(vii) at least 200 ppmw [0058] (viii) at least 300 ppmw [0059] (ix)
at least 400 ppmw [0060] (x) at least 500 ppmw [0061] (xi) at least
600 ppmw [0062] (xii) at least 700 ppmw [0063] (xiii) at least 800
ppmw [0064] (xiv) at least 900 ppmw [0065] (xv) at least 1000 ppmw
[0066] (xvi) at least 2500 ppmw [0067] (xvii) at most 5000 ppmw
[0068] (xviii) at most 10000 ppmw [0069] (xix) at most 2% wt.
[0070] (xx) at most 5% wt.
[0071] It should be noted that the base fuel may already contain
minor amounts of fuel additives, such as alkyl benzenes or alkyl
naphthenates, and the amount of at least 10 ppmw, and each of the
amounts listed in (i)-(xx) above is in addition to any minor
amounts of such fuel additives which may already be present in the
base fuel.
[0072] The liquid fuel compositions of the present invention
further comprise, as an essential component, a second fuel additive
which is selected from one or more friction modifiers.
[0073] Preferably, the amount of the second fuel additive in the
liquid fuel composition of the present invention is at least 10
ppmw (parts per million by weight), based on the overall weight of
the liquid fuel composition. More preferably, the amount of second
fuel additive present in the liquid fuel composition of the present
invention additionally accords with one or more of the parameters
(i) to (xvi) listed below: [0074] (i) at least 25 ppmw [0075] (ii)
at least 50 ppmw [0076] (iii) at least 75 ppmw [0077] (iv) at least
100 ppmw [0078] (v) at least 150 ppmw [0079] (vi) at least 200 ppmw
[0080] (vii) at least 300 ppmw [0081] (viii) at least 400 ppmw
[0082] (ix) at least 500 ppmw [0083] (x) at least 750 ppmw [0084]
(xi) at least 1000 ppmw [0085] (xii) at least 2500 ppmw [0086]
(xiii) at most 5000 ppmw [0087] (xiv) at most 10000 ppmw [0088]
(xv) at most 2% wt. [0089] (xvi) at most 5% wt.
[0090] Suitable friction modifiers for use herein include esters or
nitrogen derivatives of alkoxyamines (eg diethanolamine (DEA),
aminoethylethanolamine(AEEA)); poly(hydroxycarboxylic) acid amide
salt derivatives; poly(hydroxycarboxylic acid) derivatives having a
terminal acid group e.g. poly-12-hydroxystearic acid;
poly(hydroxycarboxylic acid) derivatives e.g.
poly-12-hydroxystearate esters; polyetheramines; esters or nitrogen
derivatives of hydroxy polycarboxylic acids (eg tartaric acid,
citric acid); esters of alkylsuccinic acids eg
dodecenylsuccinnates, polyisobutenylsuccinates; nitrogen
derivatives of carboxylic acids, eg amine salts; esters of
carboxylic acids (eg glycerol esters, glycerol mono oleate eg
Priolube 1407 from Croda Chemicals); alkoxylated alcohols eg
ethoxylated alcohols, propoxylated alcohols, butoxylated alcohols,
such as commercially available under the NEODOL tradename from
Shell Chemicals; alkoxylated amines eg ethoxylated amines,
propoxylated amines, butoxylated amines such as those commercially
from Akzo-Nobel under the tradename Ethomeen and Propomeen;
alkoxylated amides or esters, eg propoxylated ester and/or amides
of alkyl DEA or alkyl AEEA.
[0091] Preferred friction modifiers for use herein are
hyperdispersants selected from poly(hydroxycarboxylic) acid amide
salt derivatives, poly(hydroxycarboxylic acid) derivatives having a
terminal acid group, poly(hydroxycarboxylic acid) derivatives, and
polyetheramines; nitrogen derivatives of alkoxyamines, alkoxylated
amides or esters; and alkoxylated amines.
[0092] Examples of suitable friction modifiers for use herein can
be found in the following patent publications: U.S. Pat. No.
7,435,272, U.S. Pat. No. 6,866,690, WO2002/079353, WO2010/05921,
WO2009/50256, WO2010/05720, WO2002/79353, WO2010/139994,
WO97/45507, WO2002/02720, WO2010/012756, WO2010/012763, and PCT
applications PCT/EP2010/070762 and PCT/EP2010/070762.
[0093] Suitable types of hyperdispersants for use herein include
those disclosed in WO2010/012756, WO2010/012763, PCT application
number PCT/EP2010/070723 and PCT/EP2010/070762.
[0094] A preferred type of hyperdispersant for use herein are
poly(hydroxycarboxylic acid) amide salt derivatives having formula
(III):
[Y--CO[O-A-CO].sub.n--Z.sub.r--R.sup.+].sub.mpX.sup.q- (III)
[0095] wherein Y is hydrogen or optionally substituted hydrocarbyl
group, A is a divalent optionally substituted hydrocarbyl group, n
is from 1 to 100, m is from 1 to 4, q is from 1 to 4 and p is an
integer such that pq=m, Z is an optionally substituted divalent
bridging group which is attached to the carbonyl group through a
nitrogen atom, r is 0 or 1, R.sup.+ is an ammonium group and
X.sup.q- is an anion.
[0096] R.sup.+ may be a primary, secondary, tertiary or quaternary
ammonium group. R.sup.+ is preferably a quaternary ammonium
group.
[0097] In formula (III), A is preferably a divalent straight chain
or branched hydrocarbyl group as hereafter described for formulae
(I) and (II) below.
[0098] That is to say, in formula (III), A is preferably an
optionally substituted aromatic, aliphatic or cycloaliphatic
straight chain or branched divalent hydrocarbyl group. More
preferably, A is an arylene, alkylene or alkenylene group, in
particular an arylene, alkylene or alkenylene group containing in
the range of from 4 to 25 carbon atoms, more preferably in the
range of from 6 to 25 carbon atoms, more preferably in the range of
from 8 to 24 carbon atoms, more preferably in the range of from 10
to 22 carbon atoms, and most preferably in the range of from 12 to
20 carbon atoms.
[0099] Preferably, in said compound of formula (III), there are at
least 4 carbon atoms, more preferably at least 6 carbon atoms, and
even more preferably in the range of from 8 to 14 carbon atoms
connected directly between the carbonyl group and the oxygen atom
derived from the hydroxyl group.
[0100] In the compound of formula (III), the optional substituents
in the group A are preferably selected from hydroxy, halo or alkoxy
groups, especially C.sub.1-4 alkoxy groups.
[0101] In formula (III) (and formula (I)), n is in the range of
from 1 to 100. Preferably, the lower limit of the range for n is 1,
more preferably 2, even more preferably 3; preferably the upper
limit of the range for n is 100, more preferably 60, more
preferably 40, more preferably 20, and even more preferably 10
(i.e. n may be selected from any of the following ranges: from 1 to
100; from 2 to 100; from 3 to 100; from 1 to 60; from 2 to 60; from
3 to 60; from 1 to 40; from 2 to 40; from 3 to 40; from 1 to 20;
from 2 to 20; from 3 to 20; from 1 to 10; from 2 to 10; and, from 3
to 10).
[0102] In formula (III), Y is preferably an optionally substituted
hydrocarbyl group as hereinafter described for formula (I).
[0103] That is to say, the optionally substituted hydrocarbyl group
Y in formula (III) is preferably aryl, alkyl or alkenyl containing
up to 50 carbon atoms, more preferably in the range of from 7 to 25
carbon atoms. For example, the optionally substituted hydrocarbyl
group Y may be conveniently selected from heptyl, octyl, undecyl,
lauryl, heptadecyl, heptadenyl, heptadecadienyl, stearyl, oleyl and
linoleyl.
[0104] Other examples of said optionally substituted hydrocarbyl
group Y in formula (III) herein include C.sub.4-8 cycloalkyls such
as cyclohexyl; polycycloalkyls such as polycyclic terpenyl groups
which are derived from naturally occurring acids such as abietic
acid; aryls such as phenyl; aralkyls such as benzyl; and polyaryls
such as naphthyl, biphenyl, stibenzyl and phenylmethylphenyl.
[0105] In the present invention, the optionally substituted
hydrocarbyl group Y in formula (III) may contain one or more
functional groups such as carbonyl, carboxyl, nitro, hydroxy, halo,
alkoxy, amino, preferably tertiary amino (no N--H linkages), oxy,
cyano, sulphonyl and sulphoxyl. The majority of the atoms, other
than hydrogen, in substituted hydrocarbyl groups are generally
carbon, with the heteroatoms (e.g., oxygen, nitrogen and sulphur)
generally representing only a minority, about 33% or less, of the
total non-hydrogen atoms present.
[0106] Those skilled in the art will appreciate that functional
groups such as hydroxy, halo, alkoxy, nitro and cyano in a
substituted hydrocarbyl group Y will displace one of the hydrogen
atoms of the hydrocarbyl, whilst functional groups such as
carbonyl, carboxyl, tertiary amino (--N--), oxy, sulphonyl and
sulphoxyl in a substituted hydrocarbyl group will displace a --CH--
or --CH.sub.2-- moiety of the hydrocarbyl.
[0107] More preferably, the hydrocarbyl group Y in formula (III) is
unsubstituted or substituted by a group selected from hydroxy, halo
or alkoxy group, even more preferably C.sub.1-4 alkoxy.
[0108] Most preferably, the optionally substituted hydrocarbyl
group Y in formula (III) is a stearyl group, 12-hydroxystearyl
group, an oleyl group or a 12-hydroxyoleyl group, and that derived
from naturally occurring oil such as tall oil fatty acid.
[0109] In formula (III), Z is an optionally substituted divalent
bridging group, preferably of the formula
--X.sup.Z--B--Y.sup.Z.sub.q--, wherein X.sup.Z is selected from
oxygen, sulphur or a group of the formula --NR.sup.1--, wherein
R.sup.1 is as described below, B is as described below, Y.sup.Z is
selected from oxygen or a group of the formula --NR.sup.1--,
wherein R.sup.1 is as described below, and q is 0 or 1. If q is 1
and both X.sup.Z and Y.sup.z are groups of the formula
--NR.sup.1--, then the two R.sup.1 groups may form a single
hydrocarbyl group linking the two nitrogen atoms.
[0110] In formula (III), Z is preferably an optionally substituted
divalent bridging group represented by formula (IV)
##STR00001##
[0111] wherein R.sup.1 is hydrogen or a hydrocarbyl group and B is
an optionally substituted alkylene group.
[0112] Examples of hydrocarbyl groups that may represent R.sup.1
include methyl, ethyl, n-propyl, n-butyl and octadecyl.
[0113] Examples of optionally substituted alkylene groups that may
represent B include ethylene, trimethylene, tetramethylene and
hexamethylene.
[0114] Examples of preferred Z moieties in formula (III) include
--NHCH.sub.2CH.sub.2--, --NHCH.sub.2C(CH.sub.3).sub.2CH.sub.2-- and
--NH(CH.sub.2).sub.3--.
[0115] In formula (III), r is preferably 1, i.e. the
poly(hydroxycarboxylic acid) amide salt derivative having formula
(III) must contain the optionally substituted divalent bridging
group Z.
[0116] Preferably, R.sup.+ may be represented by formula (V)
##STR00002##
[0117] wherein R.sup.2, R.sup.3 and R.sup.4 may be selected from
hydrogen and alkyl groups such as methyl.
[0118] The anion X.sup.q- of the compound of formula (III) is not
critical and can be any anion (or mixture of anions) suitable to
balance the positive charge of the poly(hydroxycarboxylic acid)
amide cation.
[0119] The anion X.sup.q- of the compound of formula (III) may
conveniently be a sulphur-containing anion, such as an anion
selected from sulphate and sulphonate anions.
[0120] However, since it is desirable to maintain a low sulphur
content in gasoline and diesel fuels, the use of
non-sulphur-containing anions in the compounds of formula (III) may
be desirable depending upon the concentration of sulphur in the
liquid base fuel and/or the desired concentration of sulphur in the
liquid fuel composition containing the one or more
poly(hydroxycarboxylic acid) amide salt derivatives.
[0121] Therefore, the anion X.sup.q- of the compound of formula
(III) can also be any non-sulphur-containing anion (or mixture of
anions) suitable to balance the positive charge of the
poly(hydroxycarboxylic acid) amide cation, such as a
non-sulphur-containing organic anion or a non-sulphur-containing
inorganic anion.
[0122] Non-limiting examples of suitable anions are OH.sup.-,
CH.sup.-, NH.sub.3, HCO.sub.3, HCOO.sup.-, CH.sub.3COO.sup.-,
H.sup.-, BO.sub.3.sup.3-, CO.sub.3.sup.2-,
C.sub.2H.sub.3O.sub.2.sup.-, HCO.sup.2-, C.sub.2O.sub.4.sup.2-,
HC.sub.2O.sub.4.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-, N.sup.3-,
NH.sub.2.sup.-, O.sup.2-, O.sub.2.sup.2-, BeF.sub.3.sup.-, F.sup.-,
Na.sup.-, [Al(H.sub.2O).sub.2 (OH).sub.4].sup.-, SiO.sub.3.sup.2-,
SiF.sub.6.sup.2-, H.sub.2PO.sub.4.sup.-, P.sup.3-, PO.sub.4.sup.3-,
HPO.sub.4.sup.2-, Cl.sup.-, ClO.sub.3.sup.-, ClO.sub.4.sup.-,
ClO.sup.-, KO.sup.-, SbOH.sub.6.sup.-, SnCl.sub.6.sup.2-,
[SnTe4].sup.4-, CrO.sub.4.sup.2-, Cr.sub.2O.sub.7.sup.2-,
MnO.sub.4.sup.-, NiCl.sub.6.sup.2-,
[Cu(CO.sub.3).sub.2(OH).sub.2].sup.4-, AsO.sub.4.sup.3-, Br.sup.-,
BrO.sub.3.sup.-, IO.sub.3.sup.-, I.sup.-, CN.sup.-, OCN.sup.-,
etc.
[0123] Suitable anions may also include anions derived from
compounds containing a carboxylic acid group (e.g. a carboxylate
anion), anions derived from compounds containing a hydroxyl group
(e.g. an alkoxide, phenoxide or enolate anion), nitrogen based
anions such as nitrate and nitrite, phosphorus based anions such as
phosphates and phosphonates, or mixtures thereof.
[0124] Non-limiting examples of suitable anions derived from
compounds containing a carboxylic acid group include acetate,
oleate, salicylate anions, and mixtures thereof.
[0125] Non-limiting examples of suitable anions derived from
compounds containing a hydroxyl group include phenate anions, and
mixtures thereof.
[0126] In a preferred embodiment of the present invention, the
anion X.sup.q- is a non-sulfur-containing anion selected from the
group consisting of OH, a phenate group, a salicylate group, an
oleate group and an acetate group; more preferably the anion
X.sup.q- is OH.
[0127] The one or more poly(hydroxycarboxylic acid) amide salt
derivatives may be obtained by reaction of an amine and a
poly(hydroxycarboxylic acid) of formula (I)
Y--CO[O-A-CO].sub.n--OH (I)
wherein Y is hydrogen or optionally substituted hydrocarbyl group,
A is a divalent optionally substituted hydrocarbyl group and n is
from 1 to 100, with an acid or a quaternizing agent.
[0128] As used herein in relation to formulae (I), (II), (III),
(IV), (V), (VI) and (VII), the term "hydrocarbyl" represents a
radical formed by removal of one or more hydrogen atoms from a
carbon atom of a hydrocarbon (not necessarily the same carbon atoms
in case more hydrogen atoms are removed).
[0129] Hydrocarbyl groups may be aromatic, aliphatic, acyclic or
cyclic groups. Preferably, hydrocarbyl groups are aryl, cycloalkyl,
alkyl or alkenyl, in which case they may be straight-chain or
branched-chain groups.
[0130] Representative hydrocarbyl groups include phenyl, naphthyl,
methyl, ethyl, butyl, pentyl, methylpentyl, hexenyl, dimethylhexyl,
octenyl, cyclooctenyl, methylcyclooctenyl, dimethylcyclooctyl,
ethylhexyl, octyl, isooctyl, dodecyl, hexadecenyl, eicosyl,
hexacosyl, triacontyl and phenylethyl.
[0131] In the present invention, the phrase "optionally substituted
hydrocarbyl" is used to describe hydrocarbyl groups optionally
containing one or more "inert" heteroatom-containing functional
groups. By "inert" is meant that the functional groups do not
interfere to any substantial degree with the function of the
compound.
[0132] The optionally substituted hydrocarbyl group Y in formula
(I) herein is preferably aryl, alkyl or alkenyl containing up to 50
carbon atoms, more preferably in the range of from 7 to 25 carbon
atoms. For example, the optionally substituted hydrocarbyl group Y
may be conveniently selected from heptyl, octyl, undecyl, lauryl,
heptadecyl, heptadenyl, heptadecadienyl, stearyl, oleyl and
linoleyl.
[0133] Other examples of said optionally substituted hydrocarbyl
group Y in formula (I) herein include C.sub.4-8 cycloalkyls such as
cyclohexyl; polycycloalkyls such as polycyclic terpenyl groups
which are derived from naturally occurring acids such as abietic
acid; aryls such as phenyl; aralkyls such as benzyl; and polyaryls
such as naphthyl, biphenyl, stibenzyl and phenylmethylphenyl.
[0134] In the present invention, the optionally substituted
hydrocarbyl group Y may contain one or more functional groups such
as carbonyl, carboxyl, nitro, hydroxy, halo, alkoxy, tertiary amino
(no N--H linkages), oxy, cyano, sulphonyl and sulphoxyl. The
majority of the atoms, other than hydrogen, in substituted
hydrocarbyl groups are generally carbon, with the heteroatoms
(e.g., oxygen, nitrogen and sulphur) generally representing only a
minority, about 33% or less, of the total non-hydrogen atoms
present.
[0135] Those skilled in the art will appreciate that functional
groups such as hydroxy, halo, alkoxy, nitro and cyano in a
substituted hydrocarbyl group Y will displace one of the hydrogen
atoms of the hydrocarbyl, whilst functional groups such as
carbonyl, carboxyl, tertiary amino (--N--), oxy, sulphonyl and
sulphoxyl in a substituted hydrocarbyl group will displace a --CH--
or --CH.sub.2-- moiety of the hydrocarbyl.
[0136] The hydrocarbyl group Y in formula (I) is more preferably
unsubstituted or substituted by a group selected from hydroxy, halo
or alkoxy group, even more preferably C.sub.1-4 alkoxy.
[0137] Most preferably, the optionally substituted hydrocarbyl
group Y in formula (I) is a stearyl group, 12-hydroxystearyl group,
an oleyl group, a 12-hydroxyoleyl group or a group derived from
naturally occurring oil such as tall oil fatty acid.
[0138] In one embodiment of the present invention, at least one of,
or all of, the one or more poly(hydroxycarboxylic acid) amide salt
derivatives of formula (III) are sulphur-containing
poly(hydroxycarboxylic acid) amide salt derivatives.
[0139] In such an embodiment, said one or more
poly(hydroxycarboxylic acid) amide salt derivatives preferably have
a sulphur content of at most 2.5 wt. %, such as a sulphur content
in the range of from 0.1 to 2.0 wt. %, conveniently in the range of
from 0.6 to 1.2 wt. % sulphur, as measured by ICP-AES, based on the
total weight of said poly(hydroxycarboxylic acid) amide salt
derivatives.
[0140] In another embodiment of the present invention, the one or
more poly(hydroxycarboxylic acid) amide salt derivatives are
non-sulphur-containing poly(hydroxycarboxylic acid) amide salt
derivatives.
[0141] The preparation of poly(hydroxycarboxylic acid) and its
amide or other derivatives is known and is described, for instance,
in EP 0 164 817, WO 95/17473, WO 96/07689, U.S. Pat. No. 5,536,445,
GB 2 001 083, GB 1 342 746, GB 1 373 660, U.S. Pat. No. 5,000,792
and U.S. Pat. No. 4,349,389.
[0142] The poly(hydroxycarboxylic acid)s of formula (I) may be made
by the interesterification of one or more hydroxycarboxylic acids
of formula (II)
HO-A-COOH (II)
[0143] wherein A is a divalent optionally substituted hydrocarbyl
group, optionally in the presence of a catalyst according to well
known methods. Such methods are described, for example, in U.S.
Pat. No. 3,996,059, GB 1 373 660 and GB 1 342 746.
[0144] The chain terminator in said interesterification may be a
non-hydroxycarboxylic acid.
[0145] The hydroxyl group in the hydroxycarboxylic acid and the
carboxylic acid group in the hydroxycarboxylic acid or the
non-hydroxycarboxylic acid may be primary, secondary or tertiary in
character.
[0146] The interesterification of the hydroxycarboxylic acid and
the non-hydroxycarboxylic acid chain terminator may be effected by
heating the starting materials, optionally in a suitable
hydrocarbon solvent such as toluene or xylene, and azeotroping off
the formed water. The reaction may be carried out at a temperature
up to -250.degree. C., conveniently at the reflux temperature of
the solvent.
[0147] Where the hydroxyl group in the hydroxycarboxylic acid is
secondary or tertiary, the temperature employed should not be so
high as to lead to dehydration of the acid molecule.
[0148] Catalysts for the interesterification, such as
p-toluenesulphonic acid, zinc acetate, zirconium naphthenate or
tetrabutyl titanate, may be included, with the objective of either
increasing the rate of reaction at a given temperature or of
reducing the temperature required for a given rate of reaction.
[0149] In the compounds of formulae (I) and (II), A is preferably
an optionally substituted aromatic, aliphatic or cycloaliphatic
straight chain or branched divalent hydrocarbyl group. Preferably,
A is an arylene, alkylene or alkenylene group, in particular an
arylene, alkylene or alkenylene group containing in the range of
from 4 to 25 carbon atoms, more preferably in the range of from 6
to 25 carbon atoms, more preferably in the range of from 8 to 24
carbon atoms, more preferably in the range of from 10 to 22 carbon
atoms, and most preferably in the range of from 12 to 20 carbon
atoms.
[0150] Preferably, in said compounds of formulae (I) and (II),
there are at least 4 carbon atoms, more preferably at least 6
carbon atoms, and even more preferably in the range of from 8 to 14
carbon atoms connected directly between the carbonyl group and the
oxygen atom derived from the hydroxyl group.
[0151] In the compounds of formulae (I) and (II), the optional
substituents in the group A are preferably selected from hydroxy,
halo or alkoxy groups, more preferably C.sub.1-4 alkoxy groups.
[0152] The hydroxyl group in the hydroxycarboxylic acids of formula
(II) is preferably a secondary hydroxyl group.
[0153] Examples of suitable hydroxycarboxylic acids are
9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic
acid, 12-hydroxy-9-oleic acid (ricinoleic acid), 6-hydroxycaproic
acid, preferably 12-hydroxystearic acid. Commercial
12-hydroxystearic acid (hydrogenated castor oil fatty acid)
normally contains up to 15% wt of stearic acid and other
non-hydroxycarboxylic acids as impurities and can conveniently be
used without further admixture to produce a polymer of molecular
weight about 1000-2000.
[0154] Where the non-hydroxycarboxylic acid is introduced
separately to the reaction, the proportion which is required in
order to produce a polymer or oligomer of a given molecular weight
can be determined either by simple experiment or by calculation by
the person skilled in the art.
[0155] The group (--O-A-CO--) in the compounds of formulae (I) and
(II) is preferably a 12-oxystearyl group, 12-oxyoleyl group or a
6-oxycaproyl group.
[0156] Preferred poly(hydroxycarboxylic acid)s of formula (I) for
reaction with amine include poly(hydroxystearic acid) and
poly(hydroxyoleic acid).
[0157] The amines which react with poly(hydroxycarboxylic acid)s of
formula (I) to form poly(hydroxycarboxylic acid) amide
intermediates may include those defined in WO 97/41092.
[0158] For example, various amines and their preparations are
described in U.S. Pat. No. 3,275,554, U.S. Pat. No. 3,438,757, U.S.
Pat. No. 3,454,555, U.S. Pat. No. 3,565,804, U.S. Pat. No.
3,755,433 and U.S. Pat. No. 3,822,209.
[0159] The amine reactant is preferably a diamine, a triamine or a
polyamine.
[0160] Preferred amine reactants are diamines selected from
ethylenediamine, N,N-dimethyl-1,3-propanediamine, triamines and
polyamines selected from dietheylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine and
tris(2-aminoethyl)amine.
[0161] The amidation between the amine reactant and the
(poly(hydroxycarboxylic acid) of formula (I) may be carried out
according to methods known to those skilled in the art, by heating
the poly(hydroxycarboxylic acid) with the amine reactant,
optionally in a suitable hydrocarbon solvent such as toluene or
xylene, and azeotroping off the formed water. Said reaction may be
carried out in the presence of a catalyst such as
p-toluenesulphonic acid, zinc acetate, zirconium naphthenate or
tetrabutyl titanate.
[0162] Various patent documents disclose poly(hydroxycarboxylic
acid) amide derivatives.
[0163] For instance, GB 1 373 660 discloses poly(hydroxycarboxylic
acid) amide derivatives with amines such as
3-dimethylaminopropylamine and ethylenediamine for use as
dispersing agents in dispersions of pigments in organic
liquids.
[0164] GB 2 001 083 discloses poly(hydroxycarboxylic acid) amide
derivatives with poly(ethyleneimine) (PEI) having a molecular
weight (MW) greater than 500 for a similar use.
[0165] In U.S. Pat. No. 5,000,792, poly(hydroxycarboxylic acid)
amide derivatives with amines of the formula of
NH.sub.2--R'--N(R'')--R'''--NH.sub.2 are disclosed for use as
pigment dispersing agent.
[0166] WO 95/17473 discloses poly(hydroxycarboxylic acid) amide
derivatives with amines such as 3-dimethylaminopropylamine,
ethylenediamine, poly(ethyleneimine) (PEI) having a molecular
weight (MW) greater than 500 and amines of the formula of
NH.sub.2--R'--N(R'')--R'''--NH.sub.2 for use in a method of
preparing a non-aqueous dispersion of copper phthalocyanine.
[0167] U.S. Pat. No. 4,349,389 discloses poly(hydroxycarboxylic
acid) amide derivatives with amines such as
3-dimethyl-aminopropylamine, poly(ethyleneimine) (PEI) having a
molecular weight (MW) greater than 500 as dispersing agent in the
preparation of a dispersible inorganic pigment composition.
[0168] EP 0 164 817 discloses poly(hydroxycarboxylic acid) amide
derivatives with polyamines (ethylenediamine, diethylenetriamine,
etc.), aminoalcohols (diethanolamine, etc.) and ester derivatives
with polyols (glycerol, etc.) for use as surfactant suitable for
stabilising dispersions of solids in organic liquids and oil/water
emulsions.
[0169] However, none of the afore-mentioned patent documents
disclose the use of one or more poly(hydroxycarboxylic acid) amide
salt derivatives as disclosed herein in fuel compositions.
[0170] The poly(hydroxycarboxylic acid) amide intermediate formed
from reaction of the amine and the poly(hydroxycarboxylic acid) of
formula (I) is reacted with an acid or a quaternizing agent to form
a salt derivative, according to well-known methods.
[0171] Acids that may be used to form the salt derivative may be
selected from organic or inorganic acids. Said acids are
conveniently selected from carboxylic acids, nitrogen-containing
organic and inorganic acids, sulphur-containing organic or
inorganic acids (such as sulphuric acid, methanesulphonic acid and
benzenesulphonic acid).
[0172] Quaternizing agents that may be used to form the salt
derivative may be selected from dimethylsulphuric acid, a dialkyl
sulphate having from 1 to 4 carbon atoms, an alkyl halide such as
methyl chloride, methyl bromide, aryl halide such as benzyl
chloride.
[0173] In a preferred embodiment, the quaternizing agent is a
sulphur-containing quaternizing agent, in particular
dimethylsulphuric acid or an dialkyl sulphate having from 1 to 4
carbon atoms. The quaternizing agent is preferably dimethyl
sulphate.
[0174] Quaternization is a well-known method in the art. For
example, quaternization using dimethyl sulphate is described in
U.S. Pat. No. 3,996,059, U.S. Pat. No. 4,349,389 and GB 1 373
660.
[0175] Poly(hydroxycarboxylic acid) amide salt derivatives that are
preferred in the present invention are those which each have a TBN
(total base number) value of less than 10 mg.KOH/g, as measured by
ASTM D 4739. More preferably, the poly(hydroxycarboxylic acid)
amide salt derivatives each have a TBN value of less than 5
mg.KOH/g, most preferably 2 mg.KOH/g or less, as measured by ASTM D
4739.
[0176] Examples of poly(hydroxycarboxylic acid) amide salt
derivatives having a formula (III) that are available commercially
include that available from Lubrizol under the trade designation
"SOLSPERSE 17000" (a reaction product of poly(12-hydroxystearic
acid) with N,N-dimethyl-1,3-propanediamine and dimethyl sulphate)
and those available under the trade designations "CH-5" and "CH-7"
from Shanghai Sanzheng Polymer Company.
[0177] Another type of hyperdispersant which is suitable for use
herein is poly(hydroxycarboxylic acid) derivative having a terminal
acid group having formula (Va):
[Y--CO[O-A-CO].sub.n--Z.sub.r].sub.s--X (Va)
[0178] wherein Y, A, Z and r have the same definitions as given
above for formula (III), including any preferences and optional
substituents thereof, m is 1 or 2, and X is terminal acid group or
a group carrying a terminal acid group, wherein the terminal acid
group is selected from carboxylic acid, carboxymethyl, sulphate,
sulphonate, phosphate and phosphonate.
[0179] Preferably, in said compound of formula (Va), there are at
least 4 carbon atoms, more preferably at least 6 carbon atoms, and
even more preferably in the range of from 8 to 14 carbon atoms
connected directly between the carbonyl group and the oxygen atom
derived from the hydroxyl group.
[0180] In formula (Va), X is terminal acid group or a group
carrying a terminal acid group, wherein the terminal acid group is
selected from carboxylic acid, carboxymethyl, sulphate, sulphonate,
phosphate and phosphonate. If X is a group carrying a terminal acid
group, then preferably it is a group of the formula
--Z.sup.1--X.sup.1, wherein Z.sup.1 is a bifunctional linking
compound, such as a compound selected from a polyamine, polyol,
hydroxylamine, or a Z group as defined above, and X.sup.1 is a
terminal acid group selected from carboxylic acid, carboxymethyl,
sulphate, sulphonate, phosphate and phosphonate; more preferably,
if X is a group carrying a terminal acid group, then r in formula
(Va) is 0 and X is a group of the formula --Z.sup.1--X.sup.1.
[0181] The terminal acid group may be present in the free acid form
or in the form of a salt of the acid. If the terminal acid group is
in the form of a salt, it is can conveniently be formed by the
reaction of the terminal acid in the free acid form with a base,
for example, with ammonia, organic bases such as amines and
aminoalcohols, and inorganic bases. If the acid group in the
terminal acid group is a salt, then examples of suitable cations
include metal ions, such as sodium, potassium and calcium, and
ammonium ions, such as an ammonium ion (NH.sub.4.sup.+),
N(CH.sub.3).sub.4.sup.+, and NH(CH.sub.3).sub.4.sup.+.
[0182] The one or more poly(hydroxycarboxylic acid) derivative
having a terminal acid group may be obtained by reaction of a
poly(hydroxycarboxylic acid) of formula (I) as defined above
with:
[0183] a compound having a group reactive with the terminal
carboxylic acid group of the poly(hydroxycarboxylic acid) of
formula (I) and a terminal acid group selected from carboxylic
acid, carboxymethyl, sulphate, sulphonate, phosphate and
phosphonate;
[0184] a precursor of the terminal acid group; or
[0185] a bifunctional linking compound which is subsequently
reacted with a precursor of the terminal acid group.
[0186] Suitable compounds having a group reactive with the terminal
carboxylic acid group of the poly(hydroxycarboxylic acid) of
formula (I) and a terminal acid group selected from carboxylic
acid, carboxymethyl, sulphate, sulphonate, phosphate and
phosphonate, include alpha-amino- or alpha-hydroxy-alkane
carboxylic acids, such as glycine and glycollic acid and amino- and
hydroxy-organic sulphonic or posphonic acids, such as aminoethane
sulphonic acid; suitable precursors of the terminal acid group are
phosphorus pentoxide and sulphonyl chloride; and, suitable
bifunctional linking compounds, which can form a linking group
between the polyester and the terminal acid group, are polyamines,
polyols, hydroxyamines and Z groups as described above.
[0187] The reaction of a compound having a group reactive with the
terminal carboxylic acid group of the poly(hydroxycarboxylic acid)
of formula (I) and a terminal acid group selected from carboxylic
acid, carboxymethyl, sulphate, sulphonate, phosphate and
phosphonate;
[0188] a precursor of the terminal acid group; or
[0189] a bifunctional linking compound which is subsequently
reacted with a precursor of the terminal acid group, with a
poly(hydroxycarboxylic acid) of formula (I) is known and is
described in the art, for example in EP 0 164 817.
[0190] The poly(hydroxycarboxylic acid) derivatives having a
terminal acid group that are preferred in the present invention are
those which each have a TBN (total base number) value of less than
60 mg.KOH/g, more preferably less than 50 mg.KOH/g, even more
preferably less than 40 mg.KOH/g and most preferably less than 30
mg.KOH/g, as measured by ASTM D 4739. Conveniently, the
poly(hydroxycarboxylic acid) derivatives having a terminal acid
group may each have a TBN value of less than 5 mg.KOH/g, more
conveniently 2 mg.KOH/g or less, as measured by ASTM D 4739.
[0191] The poly(hydroxycarboxylic acid) derivatives having a
terminal acid group that are preferred in the present invention are
those which each have an acid value of less than 70 mg.KOH/g, more
preferably less than 60 mg.KOH/g, even more preferably less than 50
mg.KOH/g and most preferably less than 40 mg.KOH/g.
[0192] Another suitable hyperdispersant for use herein is a
polyetheramine having formula (VI):
##STR00003##
[0193] wherein R is an --NR.sup.1.sub.2 group where R.sup.1 is
independently selected from hydrogen and a C.sub.1-C.sub.6
hydrocarbyl group, n is in the range of from 6 to 37, m is in the
range of from 12 to 74 and p is 0 or 1.
[0194] In formula (VI), n is preferably in the range of from 8 to
24 and m is preferably in the range of from 16 to 48. In preferred
embodiments, the ratio of n:m is 1:2.
[0195] In one embodiment of the present invention, p is 1. In
another embodiment of the present invention p is 0.
[0196] In formula (VI), R is a terminal amine group wherein the
terminal amine group is selected from --NR.sup.1.sub.2, wherein
R.sup.1 is selected from hydrogen and a C.sub.1-C.sub.6 hydrocarbyl
group.
[0197] The R.sup.1 group in the terminal amine group is preferably
independently selected from hydrogen and a C.sub.1-C.sub.4
hydrocarbyl group; more preferably R.sup.1 is independently
selected from a C.sub.1-C.sub.4 alkyl group. Examples of suitable
C.sub.1-C.sub.4 alkyl groups are methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl and t-butyl groups.
[0198] Examples of suitable terminal amine groups include
--NH.sub.2, --NHCH.sub.3, --NHCH.sub.2CH.sub.3,
--NHCH.sub.2CH.sub.2CH.sub.3, --NHCH(CH.sub.3).sub.2,
--NHCH.sub.2CH.sub.2CH.sub.2CH.sub.3, --NHC(CH.sub.3).sub.3,
--N(CH.sub.3).sub.2, --N(CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3, --N(CH.sub.2CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH(CH.sub.3).sub.2)CH.sub.2CH.sub.2CH.sub.3,
--N(CH(CH.sub.3)).sub.2,
--N(CH(CH.sub.3).sub.2)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH(CH.sub.3).sub.2)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.2CH.sub.2CH.sub.3).sub.2,
N(CH.sub.2CH.sub.2CH.sub.2CH.sub.3)C(CH.sub.3).sub.3, and
--N(C(CH.sub.3).sub.3).sub.2,
[0199] In a preferred embodiment of the present invention the
terminal amine group is --N(CH.sub.2CH.sub.3).sub.2.
[0200] The preparation of compounds of formula (VI) is known and is
described in the art, for example in WO96/00440.
[0201] Examples of polyetheramines suitable for use herein include
CH-10S commercially available from Shanghai Sanzheng Polymer
Material Co. Ltd (China) and Solsperse (RTM) 20000 commercially
available from Lubrizol Advanced Materials Inc.
[0202] Another suitable hyperdispersant for use herein is a
poly(hydroxycarboxylic acid) derivative having a terminal amine
group having formula (VII):
[Y--CO[O-A-CO].sub.n--Z.sub.p].sub.m--X (VII)
[0203] wherein Y, A and n are as defined above for formula (III),
including any preferences and optional substituents, m is 1 or 2, Z
is an optionally substituted divalent bridging group, p is from 0
to 10, and X is terminal amine group or a group carrying a terminal
amine group, wherein the terminal amine group is selected from
--NR.sup.1.sub.2, wherein R.sup.1 is independently selected from
hydrogen and a C.sub.1-C.sub.6 hydrocarbyl group.
[0204] In formula (VII), p is selected from 0 to 10, preferably p
is selected from 0 to 8, more preferably p is selected from 0 to 6.
In one embodiment of the present invention, p is at least 1 (i.e. p
is selected from 1 to 10, from 1 to 8, or from 1 to 6), or at least
2 (i.e. p is selected from 2 to 10, from 2 to 8, or from 2 to
6).
[0205] In formula (VII), X is terminal amine group or a group
carrying a terminal amine group, wherein the terminal amine group
is selected from --NR.sup.1.sub.2, wherein R.sup.1 is selected from
hydrogen and a C.sub.1-C.sub.6 hydrocarbyl group. If X is a group
carrying a terminal amine group, then preferably it is a group of
the formula --Z.sup.1--X.sup.1, wherein Z.sup.1 is a bifunctional
linking compound, such as a compound selected from a polyamine,
polyol, hydroxylamine, or a Z group as defined above, and X.sup.1
is a terminal amine group selected from --NR.sup.1.sub.2, wherein
R.sup.1 is selected from hydrogen and a C.sub.1-C.sub.6 hydrocarbyl
group, if X is a group carrying a terminal acid group, then p in
formula (VII) is 0 and X is a group of the formula
--Z.sup.1--X.sup.1.
[0206] The R.sup.1 group in the terminal amine group is preferably
independently selected from hydrogen and a C.sub.1-C.sub.4
hydrocarbyl group; more preferably R.sup.1 is independently
selected from hydrogen and a C.sub.1-C.sub.4 alkyl group. Examples
of suitable C.sub.1-C.sub.4 alkyl groups are methyl, ethyl,
n-propyl, i-propyl, n-butyl, i-butyl and t-butyl groups.
[0207] Examples of suitable terminal amine groups include
--NH.sub.2, --NHCH.sub.3, --NHCH.sub.2CH.sub.3,
--NHCH.sub.2CH.sub.2CH.sub.3, --NHCH(CH.sub.3).sub.2,
--NHCH.sub.2CH.sub.2CH.sub.2CH.sub.3, --NHC(CH.sub.3).sub.3,
--N(CH.sub.3).sub.2, --N(CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3, --N(CH.sub.2CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH(CH.sub.3).sub.2)CH.sub.2CH.sub.2CH.sub.3,
--N(CH(CH.sub.3)).sub.2,
--N(CH(CH.sub.3).sub.2)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH(CH.sub.3).sub.2)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3)CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3).sub.2,
--N(CH.sub.2CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
--N(CH.sub.2CH.sub.2CH.sub.3)C(CH.sub.3).sub.3,
--N(CH.sub.2CH.sub.2CH.sub.2CH.sub.3).sub.2,
N(CH.sub.2CH.sub.2CH.sub.2CH.sub.3)C(CH.sub.3).sub.3, and
--N(C(CH.sub.3).sub.3).sub.2.
[0208] In one embodiment of the present invention the terminal
amine group is --NH.sub.2.
[0209] The one or more poly(hydroxycarboxylic acid) derivative
having a terminal amine group may be obtained by reaction of a
poly(hydroxycarboxylic acid) of formula (I) as defined above
with:
[0210] a compound having a group reactive with the terminal
carboxylic acid group of the poly(hydroxycarboxylic acid) of
formula (I) and a terminal amine group as defined above;
[0211] a precursor of the terminal amine group; or
[0212] a bifunctional linking compound which is subsequently
reacted with a precursor of the terminal amine group.
[0213] Suitable compounds having a group reactive with the terminal
carboxylic acid group of the poly(hydroxycarboxylic acid) of
formula (I) and a terminal amine group, include unsubstituted and
substituted amines, diamines, and polyamines, examples of
substituted amines are mono-, di- and tri-alkylamines,
alkyleneamines, and alpha-amino- or alpha-hydroxy-alkane amines,
most suitably ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepennamine and
pentaethylenehexamine, most preferably tetraethylenepentamine; and,
suitable bifunctional linking compounds, which can form a linking
group between the polyester and the terminal amine group, are
polyamines, polyols, hydroxyamines and Z groups as described
above.
[0214] The reaction of a compound having a group reactive with the
terminal carboxylic acid group of the poly(hydroxycarboxylic acid)
of formula (I) and a terminal amine group;
[0215] a precursor of the terminal amine group; or
[0216] a bifunctional linking compound which is subsequently
reacted with a precursor of the terminal amine group, with a
poly(hydroxycarboxylic acid) of formula (I) is known and is
described in the art, for example in EP 0 164 817.
[0217] The poly(hydroxycarboxylic acid) derivatives having a
terminal amine group that are preferred in the present invention
are those which each have a TBN (total base number) value of at
least 100 mg.KOH/g, more preferably at least 150 mg.KOH/g, even
more preferably at least 175 mg.KOH/g and most preferably at least
200 mg.KOH/g, as measured by ASTM D 4739. The TBN may be at most
300 mg.KOH/g, preferably at most 250 mg.KOH/g.
[0218] The poly(hydroxycarboxylic acid) derivatives having a
terminal amine group that are preferred in the present invention
are those which each have an acid value of less than 20 mg.KOH/g,
more preferably less than 15 mg.KOH/g, even more preferably less
than 10 mg.KOH/g and most preferably less than 7 mg.KOH/g. The TAN
may be at least 0 mg.KOH/g.
[0219] A preferred class of friction modifiers for use herein is
nitrogen derivatives of alkoxyamines such as those disclosed in
WO2009/50287, in particular, the reaction product of oleic acid and
aminoethylethanolamine 3:1 molar ratio as disclosed in Example 4 of
WO2009/50287.
[0220] Another preferred class of friction modifiers for use herein
is alkoxylated amides or esters such as those disclosed in
WO2010/05720. An example of such a friction modifier is a
propoxylated ester of alkyl DEA as disclosed in WO2010/05720 and
commercially available from BASF.
[0221] Examples of commercially available friction modifiers
suitable for use as the second additive herein include, but are not
limited to, HiTec 6457 commercially available from Afton Chemicals;
Kerocom K3561 commercially available from BASF; OLI9000 and OL19900
commercially available from Innospec; Ultrazol 9525 and Ultrazol
9555 commercially available from Lubrizol; Neodol N23-2, Neodol
N25-7 and Neodol N91-5 commercially available from Shell Chemical;
Ethomeen T12, Ethomeen T12e, Ethomeen T15, Ethomeen O12, Ethomeen
O15, Ethomeen T20 and Ethomeen C15 commercially available from
AkzoNobel; OMA4 commercially available from AkzoNobel; Amadol 128t,
Amadol 61 and Amadol 5134 commercially available from AkzoNobel;
Solsperse 3000, Solsperse 21000, Solperse 17000, Solserse 13000,
Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 20000,
Solsperse 24000 and Solsperse 9000 commercially available from
Lubrizol; CH2C, CH1a, CH7A, CH5, CH6, CH10S, CH13 and CH3 all
commercially available from Shanghai Sanzheng Polymer Material Co.
Ltd.
[0222] The first fuel additive and second fuel additive are blended
together with any other additives e.g. additive performance
package(s) to produce an additive blend. The additive blend is then
added to a base fuel to produce a liquid fuel composition. The
amount of first fuel additive in the additive blend is preferably
in the range of from 0.1 to 99.8 wt %, by weight of the additive
blend. The amount of second fuel additive in the additive blend is
preferably in the range of from 0.1 to 99.8 wt %, by weight of the
additive blend.
[0223] The amount of performance package(s) in the additive blend
is preferably in the range of from 0.1 to 99.8 wt %, by weight of
the additive blend.
[0224] Preferably, the amount of the performance package present in
the liquid fuel composition of the present invention is in the
range of 15 ppmw (parts per million by weight) to 10% wt, based on
the overall weight of the liquid fuel composition. More preferably,
the amount of the performance package present in the liquid fuel
composition of the present invention additionally accords with one
or more of the parameters (i) to (xv) listed below: [0225] (i) at
least 100 ppmw [0226] (ii) at least 200 ppmw [0227] (iii) at least
300 ppmw [0228] (iv) at least 400 ppmw [0229] (v) at least 500 ppmw
[0230] (vi) at least 600 ppmw [0231] (vii) at least 700 ppmw [0232]
(viii) at least 800 ppmw [0233] (ix) at least 900 ppmw [0234] (x)
at least 1000 ppmw [0235] (xi) at least 2500 ppmw [0236] (xii) at
most 5000 ppmw [0237] (xiii) at most 10000 ppmw [0238] (xiv) at
most 2% wt. [0239] (xv) at most 5% wt.
[0240] In the liquid fuel compositions of the present invention, if
the base fuel used is a gasoline, then the gasoline may be any
gasoline suitable for use in an internal combustion engine of the
spark-ignition (petrol) type known in the art, including automotive
engines as well as in other types of engine such as, for example,
off road and aviation engines. The gasoline used as the base fuel
in the liquid fuel composition of the present invention may
conveniently also be referred to as `base gasoline`.
[0241] Gasolines typically comprise mixtures of hydrocarbons
boiling in the range from 25 to 230.degree. C. (EN-ISO 3405), the
optimal ranges and distillation curves typically varying according
to climate and season of the year. The hydrocarbons in a gasoline
may be derived by any means known in the art, conveniently the
hydrocarbons may be derived in any known manner from straight-run
gasoline, synthetically-produced aromatic hydrocarbon mixtures,
thermally or catalytically cracked hydrocarbons, hydro-cracked
petroleum fractions, catalytically reformed hydrocarbons or
mixtures of these.
[0242] The specific distillation curve, hydrocarbon composition,
research octane number (RON) and motor octane number (MON) of the
gasoline are not critical.
[0243] Conveniently, the research octane number (RON) of the
gasoline may be at least 80, for instance in the range of from 80
to 110, preferably the RON of the gasoline will be at least 90, for
instance in the range of from 90 to 110, more preferably the RON of
the gasoline will be at least 91, for instance in the range of from
91 to 105, even more preferably the RON of the gasoline will be at
least 92, for instance in the range of from 92 to 103, even more
preferably the RON of the gasoline will be at least 93, for
instance in the range of from 93 to 102, and most preferably the
RON of the gasoline will be at least 94, for instance in the range
of from 94 to 100 (EN 25164); the motor octane number (MON) of the
gasoline may conveniently be at least 70, for instance in the range
of from 70 to 110, preferably the MON of the gasoline will be at
least 75, for instance in the range of from 75 to 105, more
preferably the MON of the gasoline will be at least 80, for
instance in the range of from 80 to 100, most preferably the MON of
the gasoline will be at least 82, for instance in the range of from
82 to 95 (EN 25163).
[0244] Typically, gasolines comprise components selected from one
or more of the following groups; saturated hydrocarbons, olefinic
hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons.
Conveniently, the gasoline may comprise a mixture of saturated
hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and,
optionally, oxygenated hydrocarbons.
[0245] Typically, the olefinic hydrocarbon content of the gasoline
is in the range of from 0 to 40 percent by volume based on the
gasoline (ASTM D1319); preferably, the olefinic hydrocarbon content
of the gasoline is in the range of from 0 to 30 percent by volume
based on the gasoline, more preferably, the olefinic hydrocarbon
content of the gasoline is in the range of from 0 to 20 percent by
volume based on the gasoline.
[0246] Typically, the aromatic hydrocarbon content of the gasoline
is in the range of from 0 to 70 percent by volume based on the
gasoline (ASTM D1319), for instance the aromatic hydrocarbon
content of the gasoline is in the range of from 10 to 60 percent by
volume based on the gasoline; preferably, the aromatic hydrocarbon
content of the gasoline is in the range of from 0 to 50 percent by
volume based on the gasoline, for instance the aromatic hydrocarbon
content of the gasoline is in the range of from 10 to 50 percent by
volume based on the gasoline.
[0247] The benzene content of the gasoline is at most 10 percent by
volume, more preferably at most 5 percent by volume, especially at
most 1 percent by volume based on the gasoline.
[0248] The gasoline preferably has a low or ultra low sulphur
content, for instance at most 1000 ppmw (parts per million by
weight), preferably no more than 500 ppmw, more preferably no more
than 100, even more preferably no more than 50 and most preferably
no more than even 10 ppmw.
[0249] The gasoline also preferably has a low total lead content,
such as at most 0.005 g/l, most preferably being lead free--having
no lead compounds added thereto (i.e. unleaded).
[0250] When the gasoline comprises oxygenated hydrocarbons, at
least a portion of non-oxygenated hydrocarbons will be substituted
for oxygenated hydrocarbons. The oxygen content of the gasoline may
be up to 35 percent by weight (EN 1601) (e.g. ethanol per se) based
on the gasoline. For example, the oxygen content of the gasoline
may be up to 25 percent by weight, preferably up to 10 percent by
weight. Conveniently, the oxygenate concentration will have a
minimum concentration selected from any one of 0, 0.2, 0.4, 0.6,
0.8, 1.0, and 1.2 percent by weight, and a maximum concentration
selected from any one of 5, 4.5, 4.0, 3.5, 3.0, and 2.7 percent by
weight.
[0251] Examples of oxygenated hydrocarbons that may be incorporated
into the gasoline include alcohols, ethers, esters, ketones,
aldehydes, carboxylic acids and their derivatives, and oxygen
containing heterocyclic compounds. Preferably, the oxygenated
hydrocarbons that may be incorporated into the gasoline are
selected from alcohols (such as methanol, ethanol, propanol,
2-propanol, butanol, tert-butanol, iso-butanol and 2-butanol),
ethers (preferably ethers containing 5 or more carbon atoms per
molecule, e.g., methyl tert-butyl ether and ethyl tert-butyl ether)
and esters (preferably esters containing 5 or more carbon atoms per
molecule); a particularly preferred oxygenated hydrocarbon is
ethanol.
[0252] When oxygenated hydrocarbons are present in the gasoline,
the amount of oxygenated hydrocarbons in the gasoline may vary over
a wide range. For example, gasolines comprising a major proportion
of oxygenated hydrocarbons are currently commercially available in
countries such as Brazil and U.S.A., e.g. ethanol per se and E85,
as well as gasolines comprising a minor proportion of oxygenated
hydrocarbons, e.g. E10 and E5. Therefore, the gasoline may contain
up to 100 percent by volume oxygenated hydrocarbons. E100 fuels as
used in Brazil are also included herein. Preferably, the amount of
oxygenated hydrocarbons present in the gasoline is selected from
one of the following amounts: up to 85 percent by volume; up to 70
percent by volume; up to 65 percent by volume; up to 30 percent by
volume; up to 20 percent by volume; up to 15 percent by volume;
and, up to 10 percent by volume, depending upon the desired final
formulation of the gasoline. Conveniently, the gasoline may contain
at least 0.5, 1.0 or 2.0 percent by volume oxygenated
hydrocarbons.
[0253] Examples of suitable gasolines include gasolines which have
an olefinic hydrocarbon content of from 0 to 20 percent by volume
(ASTM D1319), an oxygen content of from 0 to 5 percent by weight
(EN 1601), an aromatic hydrocarbon content of from 0 to 50 percent
by volume (ASTM D1319) and a benzene content of at most 1 percent
by volume.
[0254] Also suitable for use herein are gasoline blending
components which can be derived from a biological source. Examples
of such gasoline blending components can be found in WO2009/077606,
WO2010/028206, WO2010/000761, European patent application nos.
09160983.4, 09176879.6, 09180904.6, and U.S. patent application
Ser. No. 61/312,307.
[0255] Whilst not critical to the present invention, the base
gasoline or the gasoline composition of the present invention may
conveniently include one or more optional fuel additives, in
addition to the essential fuel additive mentioned above. The
concentration and nature of the optional fuel additive(s) that may
be included in the base gasoline or the gasoline composition of the
present invention is not critical. Non-limiting examples of
suitable types of fuel additives that can be included in the base
gasoline or the gasoline composition of the present invention
include anti-oxidants, corrosion inhibitors, detergents, dehazers,
antiknock additives, metal deactivators, valve-seat recession
protectant compounds, dyes, solvents, carrier fluids, diluents and
markers. Examples of suitable such additives are described
generally in U.S. Pat. No. 5,855,629.
[0256] Conveniently, the fuel additives can be blended with one or
more solvents to form an additive concentrate, the additive
concentrate can then be admixed with the base gasoline or the
gasoline composition of the present invention.
[0257] The (active matter) concentration of any optional additives
present in the base gasoline or the gasoline composition of the
present invention is preferably up to 1 percent by weight, more
preferably in the range from 5 to 2000 ppmw, advantageously in the
range of from 300 to 1500 ppmw, such as from 300 to 1000 ppmw.
[0258] As stated above, the gasoline composition may also contain
synthetic or mineral carrier oils and/or solvents.
[0259] Examples of suitable mineral carrier oils are fractions
obtained in crude oil processing, such as brightstock or base oils
having viscosities, for example, from the SN 500-2000 class; and
also aromatic hydrocarbons, paraffinic hydrocarbons and
alkoxyalkanols. Also useful as a mineral carrier oil is a fraction
which is obtained in the refining of mineral oil and is known as
"hydrocrack oil" (vacuum distillate cut having a boiling range of
from about 360 to 500.degree. C., obtainable from natural mineral
oil which has been catalytically hydrogenated under high pressure
and isomerized and also deparaffinized).
[0260] Examples of suitable synthetic carrier oils are: polyolefins
(poly-alpha-olefins or poly(internal olefin)s), (poly)esters,
(poly)alkoxylates, polyethers, aliphatic polyether amines,
alkylphenol-started polyethers, alkylphenol-started polyether
amines and carboxylic esters of long-chain alkanols.
[0261] Examples of suitable polyolefins are olefin polymers, in
particular based on polybutene or polyisobutene (hydrogenated or
nonhydrogenated).
[0262] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyether amines used may be
poly-C.sub.2-C.sub.6-alkylene oxide amines or functional
derivatives thereof. Typical examples thereof are tridecanol
butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also polyisobutenol butoxylates and propoxylates,
and also the corresponding reaction products with ammonia.
[0263] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; suitable ester alcohols or polyols are
in particular long-chain representatives having, for example, from
6 to 24 carbon atoms. Typical representatives of the esters are
adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di-(n- or isotridecyl) phthalate.
[0264] Further suitable carrier oil systems are described, for
example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0
452 328 and EP-A-0 548 617, which are incorporated herein by way of
reference.
[0265] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having from about 5 to 35, for example
from about 5 to 30, C.sub.3-C.sub.6-alkylene oxide units, for
example selected from propylene oxide, n-butylene oxide and
isobutylene oxide units, or mixtures thereof. Non-limiting examples
of suitable starter alcohols are long-chain alkanols or phenols
substituted by long-chain alkyl in which the long-chain alkyl
radical is in particular a straight-chain or branched
C.sub.6-C.sub.18-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0266] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-10 102 913.6.
[0267] Mixtures of mineral carrier oils, synthetic carrier oils,
and mineral and synthetic carrier oils may also be used.
[0268] Any solvent and optionally co-solvent suitable for use in
fuels may be used. Examples of suitable solvents for use in fuels
include: non-polar hydrocarbon solvents such as kerosene, heavy
aromatic solvent ("solvent naphtha heavy", "Solvesso 150"),
toluene, xylene, paraffins, petroleum, white spirits, those sold by
Shell companies under the trademark "SHELLSOL", and the like.
Examples of suitable co-solvents include: polar solvents such as
esters and, in particular, alcohols (e.g. t-butanol, i-butanol,
hexanol, 2-ethylhexanol, 2-propyl heptanol, decanol, isotridecanol,
butyl glycols, and alcohol mixtures such as those sold by Shell
companies under the trade mark "LINEVOL", especially LINEVOL 79
alcohol which is a mixture of C.sub.7-9 primary alcohols, or a
C.sub.12-14 alcohol mixture which is commercially available).
[0269] Dehazers/demulsifiers suitable for use in liquid fuels are
well known in the art. Non-limiting examples include glycol
oxyalkylate polyol blends (such as sold under the trade designation
TOLAD.TM. 9312), alkoxylated phenol formaldehyde polymers,
phenol/formaldehyde or C.sub.1-18 alkylphenol/-formaldehyde resin
oxyalkylates modified by oxyalkylation with C.sub.1-18 epoxides and
diepoxides (such as sold under the trade designation TOLAD.TM.
9308), and C.sub.1-4 epoxide copolymers cross-linked with
diepoxides, diacids, diesters, diols, diacrylates, dimethacrylates
or diisocyanates, and blends thereof. The glycol oxyalkylate polyol
blends may be polyols oxyalkylated with C.sub.1-4 epoxides. The
C.sub.1-18 alkylphenol phenol/-formaldehyde resin oxyalkylates
modified by oxyalkylation with C.sub.1-18 epoxides and diepoxides
may be based on, for example, cresol, t-butyl phenol, dodecyl
phenol or dinonyl phenol, or a mixture of phenols (such as a
mixture of t-butyl phenol and nonyl phenol). The dehazer should be
used in an amount sufficient to inhibit the hazing that might
otherwise occur when the gasoline without the dehazer contacts
water, and this amount will be referred to herein as a
"haze-inhibiting amount." Generally, this amount is from about 0.1
to about 20 ppmw (e.g. from about 0.1 to about 10 ppm), more
preferably from 1 to 15 ppmw, still more preferably from 1 to 10
ppmw, advantageously from 1 to 5 ppmw based on the weight of the
gasoline.
[0270] Further customary additives for use in gasolines are
corrosion inhibitors, for example based on ammonium salts of
organic carboxylic acids, said salts tending to form films, or of
heterocyclic aromatics for nonferrous metal corrosion protection;
antioxidants or stabilizers, for example based on amines such as
phenyldiamines, e.g. p-phenylenediamine,
N,N'-di-sec-butyl-p-phenyldiamine, dicyclohexylamine or derivatives
thereof or of phenols such as 2,4-di-tert-butylphenol or
3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid; anti-static
agents; metallocenes such as ferrocene;
methylcyclopentadienylmanganese tricarbonyl; lubricity additives,
such as certain fatty acids, alkenylsuccinic esters,
bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil;
and also dyes (markers). Amines may also be added, if appropriate,
for example as described in WO 03/076554. Optionally anti valve
seat recession additives may be used such as sodium or potassium
salts of polymeric organic acids.
[0271] The gasoline compositions herein can also comprise a
detergent additive. Suitable detergent additives include those
disclosed in WO2009/50287, incorporated herein by reference.
[0272] Preferred detergent additives for use in the gasoline
composition herein typically have at least one hydrophobic
hydrocarbon radical having a number-average molecular weight (Mn)
of from 85 to 20 000 and at least one polar moiety selected
from:
[0273] (A1) mono- or polyamino groups having up to 6 nitrogen
atoms, of which at least one nitrogen atom has basic
properties;
[0274] (A6) polyoxy-C.sub.2- to -C.sub.4-alkylene groups which are
terminated by hydroxyl groups, mono- or polyamino groups, in which
at least one nitrogen atom has basic properties, or by carbamate
groups;
[0275] (A8) moieties derived from succinic anhydride and having
hydroxyl and/or amino and/or amido and/or imido groups; and/or
[0276] (A9) moieties obtained by Mannich reaction of substituted
phenols with aldehydes and mono- or polyamines.
[0277] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the base fluid,
has a number-average molecular weight (Mn) of from 85 to 20 000,
especially from 113 to 10 000, in particular from 300 to 5000.
Typical hydrophobic hydrocarbon radicals, especially in conjunction
with the polar moieties (A1), (A8) and (A9), include polyalkenes
(polyolefins), such as the polypropenyl, polybutenyl and
polyisobutenyl radicals each having Mn of from 300 to 5000,
preferably from 500 to 2500, more preferably from 700 to 2300, and
especially from 700 to 1000.
[0278] Non-limiting examples of the above groups of detergent
additives include the following:
[0279] Additives comprising mono- or polyamino groups (A1) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or conventional (i.e. having predominantly internal
double bonds) polybutene or polyisobutene having Mn of from 300 to
5000. When polybutene or polyisobutene having predominantly
internal double bonds (usually in the beta and gamma position) are
used as starting materials in the preparation of the additives, a
possible preparative route is by chlorination and subsequent
amination or by oxidation of the double bond with air or ozone to
give the carbonyl or carboxyl compound and subsequent amination
under reductive (hydrogenating) conditions. The amines used here
for the amination may be, for example, ammonia, monoamines or
polyamines, such as dimethylaminopropylamine, ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Corresponding additives based on polypropene are described in
particular in WO-A-94/24231.
[0280] Further preferred additives comprising monoamino groups (A1)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization of from 5
to 100, with nitrogen oxides or mixtures of nitrogen oxides and
oxygen, as described in particular in WO-A-97/03946.
[0281] Further preferred additives comprising monoamino groups (A1)
are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described in particular in DE-A-196 20
262.
[0282] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (A6) are preferably polyethers or polyetheramines which
are obtainable by reaction of C.sub.2- to C.sub.60-alkanols,
C.sub.6- to C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group and, in the case of the polyether-amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. In the
case of polyethers, such products also have carrier oil properties.
Typical examples of these are tridecanol butoxylates, isotridecanol
butoxylates, isononylphenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0283] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups (A8) are preferably corresponding derivatives of
polyisobutenylsuccinic anhydride which are obtainable by reacting
conventional or highly reactive polyisobutene having Mn of from 300
to 5000 with maleic anhydride by a thermal route or via the
chlorinated polyisobutene. Of particular interest are derivatives
with aliphatic polyamines such as ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Such additives are described in particular in U.S. Pat. No.
4,849,572.
[0284] Additives comprising moieties obtained by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines (A9)
are preferably reaction products of polyisobutene-substituted
phenols with formaldehyde and mono- or polyamines such as
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine or dimethylaminopropylamine. The
polyisobutenyl-substituted phenols may stem from conventional or
highly reactive polyisobutene having Mn of from 300 to 5000. Such
"polyisobutene-Mannich bases" are described in particular in
EP-A-831 141.
[0285] Preferably, the detergent additive used in the gasoline
compositions of the present invention contains at least one
nitrogen-containing detergent, more preferably at least one
nitrogen-containing detergent containing a hydrophobic hydrocarbon
radical having a number average molecular weight in the range of
from 300 to 5000. Preferably, the nitrogen-containing detergent is
selected from a group comprising polyalkene monoamines,
polyetheramines, polyalkene Mannich amines and polyalkene
succinimides. Conveniently, the nitrogen-containing detergent may
be a polyalkene monoamine.
[0286] In the liquid fuel compositions of the present invention, if
the base fuel used is a diesel fuel, then the diesel fuel used as
the base fuel in the present invention includes diesel fuels for
use in automotive compression ignition engines, as well as in other
types of engine such as for example off road, marine, railroad and
stationary engines. The diesel fuel used as the base fuel in the
liquid fuel composition of the present invention may conveniently
also be referred to as `diesel base fuel`.
[0287] The diesel base fuel may itself comprise a mixture of two or
more different diesel fuel components, and/or be additivated as
described below.
[0288] Such diesel fuels will contain one or more base fuels which
may typically comprise liquid hydrocarbon middle distillate gas
oil(s), for instance petroleum derived gas oils. Such fuels will
typically have boiling points within the usual diesel range of 150
to 400.degree. C., depending on grade and use. They will typically
have a density from 750 to 1000 kg/m.sup.3, preferably from 780 to
860 kg/m.sup.3, at 15.degree. C. (e.g. ASTM D4502 or IP 365) and a
cetane number (ASTM D613) of from 35 to 120, more preferably from
40 to 85. They will typically have an initial boiling point in the
range 150 to 230.degree. C. and a final boiling point in the range
290 to 400.degree. C. Their kinematic viscosity at 40.degree. C.
(ASTM D445) might suitably be from 1.2 to 4.5 mm.sup.2/s.
[0289] An example of a petroleum derived gas oil is a Swedish Class
1 base fuel, which will have a density from 800 to 820 kg/m.sup.3
at 15.degree. C. (SS-EN ISO 3675, SS-EN ISO 12185), a T95 of
320.degree. C. or less (SS-EN ISO 3405) and a kinematic viscosity
at 40.degree. C. (SS-EN ISO 3104) from 1.4 to 4.0 mm.sup.2/s, as
defined by the Swedish national specification EC1.
[0290] Optionally, non-mineral oil based fuels, such as biofuels or
Fischer-Tropsch derived fuels, may also form or be present in the
diesel fuel. Such Fischer-Tropsch fuels may for example be derived
from natural gas, natural gas liquids, petroleum or shale oil,
petroleum or shale oil processing residues, coal or biomass.
[0291] The amount of Fischer-Tropsch derived fuel used in the
diesel fuel may be from 0% to 100% v of the overall diesel fuel,
preferably from 5% to 100% v, more preferably from 5% to 75% v. It
may be desirable for such a diesel fuel to contain 10% v or
greater, more preferably 20% v or greater, still more preferably
30% v or greater, of the Fischer-Tropsch derived fuel. It is
particularly preferred for such diesel fuels to contain 30 to 75%
v, and particularly 30 to 70% v, of the Fischer-Tropsch derived
fuel. The balance of the diesel fuel is made up of one or more
other diesel fuel components.
[0292] Such a Fischer-Tropsch derived fuel component is any
fraction of the middle distillate fuel range, which can be isolated
from the (optionally hydrocracked) Fischer-Tropsch synthesis
product. Typical fractions will boil in the naphtha, kerosene or
gas oil range. Preferably, a Fischer-Tropsch product boiling in the
kerosene or gas oil range is used because these products are easier
to handle in for example domestic environments. Such products will
suitably comprise a fraction larger than 90 wt % which boils
between 160 and 400.degree. C., preferably to about 370.degree. C.
Examples of Fischer-Tropsch derived kerosene and gas oils are
described in EP-A-0583836, WO-A-97/14768, WO-A-97/14769,
WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648,
WO-A-01/83647, WO-A-01/83641, WO-A-00/20535, WO-A-00/20534,
EP-A-1101813, U.S. Pat. No. 5,766,274, U.S. Pat. No. 5,378,348,
U.S. Pat. No. 5,888,376 and U.S. Pat. No. 6,204,426.
[0293] The Fischer-Tropsch product will suitably contain more than
80 wt % and more suitably more than 95 wt % iso and normal
paraffins and less than 1 wt % aromatics, the balance being
naphthenics compounds. The content of sulphur and nitrogen will be
very low and normally below the detection limits for such
compounds. For this reason the sulphur content of a diesel fuel
composition containing a Fischer-Tropsch product may be very
low.
[0294] The diesel fuel composition preferably contains no more than
5000 ppmw sulphur, more preferably no more than 500 ppmw, or no
more than 350 ppmw, or no more than 150 ppmw, or no more than 100
ppmw, or no more than 70 ppmw, or no more than 50 ppmw, or no more
than 30 ppmw, or no more than 20 ppmw, or most preferably no more
than 10 ppmw sulphur.
[0295] Other diesel fuel components for use herein include the
so-called "biofuels" which derive from biological materials.
Examples include fatty acid alkyl esters (FAAE). Examples of such
components can be found in WO2008/135602.
[0296] The diesel base fuel may itself be additivated
(additive-containing) or unadditivated (additive-free). If
additivated, e.g. at the refinery, it will contain minor amounts of
one or more additives selected for example from anti-static agents,
pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate
copolymers or acrylate/maleic anhydride copolymers), lubricity
additives, antioxidants and wax anti-settling agents.
[0297] Detergent-containing diesel fuel additives are known and
commercially available. Such additives may be added to diesel fuels
at levels intended to reduce, remove, or slow the build-up of
engine deposits.
[0298] Examples of detergents suitable for use in diesel fuel
additives for the present purpose include polyolefin substituted
succinimides or succinamides of polyamines, for instance
polyisobutylene succinimides or polyisobutylene amine succinamides,
aliphatic amines, Mannich bases or amines and polyolefin (e.g.
polyisobutylene) maleic anhydrides. Succinimide dispersant
additives are described for example in GB-A-960493, EP-A-0147240,
EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808.
Particularly preferred are polyolefin substituted succinimides such
as polyisobutylene succinimides.
[0299] The diesel fuel additive mixture may contain other
components in addition to the detergent. Examples are lubricity
enhancers; dehazers, e.g. alkoxylated phenol formaldehyde polymers;
anti-foaming agents (e.g. polyether-modified polysiloxanes);
ignition improvers (cetane improvers) (e.g. 2-ethylhexyl nitrate
(EHN), cyclohexyl nitrate, di-tert-butyl peroxide and those
disclosed in U.S. Pat. No. 4,208,190 at column 2, line 27 to column
3, line 21); anti-rust agents (e.g. a propane-1,2-diol semi-ester
of tetrapropenyl succinic acid, or polyhydric alcohol esters of a
succinic acid derivative, the succinic acid derivative having on at
least one of its alpha-carbon atoms an unsubstituted or substituted
aliphatic hydrocarbon group containing from 20 to 500 carbon atoms,
e.g. the pentaerythritol diester of polyisobutylene-substituted
succinic acid); corrosion inhibitors; reodorants; anti-wear
additives; anti-oxidants (e.g. phenolics such as
2,6-di-tert-butylphenol, or phenylenediamines such as
N,N'-di-sec-butyl-p-phenylenediamine); metal deactivators;
combustion improvers; static dissipator additives; cold flow
improvers; and wax anti-settling agents.
[0300] The diesel fuel additive mixture may contain a lubricity
enhancer, especially when the diesel fuel composition has a low
(e.g. 500 ppmw or less) sulphur content. In the additivated diesel
fuel composition, the lubricity enhancer is conveniently present at
a concentration of less than 1000 ppmw, preferably between 50 and
1000 ppmw, more preferably between 70 and 1000 ppmw. Suitable
commercially available lubricity enhancers include ester- and
acid-based additives. Other lubricity enhancers are described in
the patent literature, in particular in connection with their use
in low sulphur content diesel fuels, for example in: [0301] the
paper by Danping Wei and H. A. Spikes, "The Lubricity of Diesel
Fuels", Wear, III (1986) 217-235; [0302] WO-A-95/33805--cold flow
improvers to enhance lubricity of low sulphur fuels; [0303] U.S.
Pat. No. 5,490,864--certain dithiophosphoric diester-dialcohols as
anti-wear lubricity additives for low sulphur diesel fuels; and
[0304] WO-A-98/01516--certain alkyl aromatic compounds having at
least one carboxyl group attached to their aromatic nuclei, to
confer anti-wear lubricity effects particularly in low sulphur
diesel fuels.
[0305] It may also be preferred for the diesel fuel composition to
contain an anti-foaming agent, more preferably in combination with
an anti-rust agent and/or a corrosion inhibitor and/or a lubricity
enhancing additive.
[0306] Unless otherwise stated, the (active matter) concentration
of each such optional additive component in the additivated diesel
fuel composition is preferably up to 10000 ppmw, more preferably in
the range from 0.1 to 1000 ppmw, advantageously from 0.1 to 300
ppmw, such as from 0.1 to 150 ppmw.
[0307] The (active matter) concentration of any dehazer in the
diesel fuel composition will preferably be in the range from 0.1 to
20 ppmw, more preferably from 1 to 15 ppmw, still more preferably
from 1 to 10 ppmw, and especially from 1 to 5 ppmw. The (active
matter) concentration of any ignition improver present will
preferably be 2600 ppmw or less, more preferably 2000 ppmw or less,
even more preferably 300 to 1500 ppmw. The (active matter)
concentration of any detergent in the diesel fuel composition will
preferably be in the range from 5 to 1500 ppmw, more preferably
from 10 to 750 ppmw, most preferably from 20 to 500 ppmw.
[0308] In the case of a diesel fuel composition, for example, the
fuel additive mixture will typically contain a detergent,
optionally together with other components as described above, and a
diesel fuel-compatible diluent, which may be a mineral oil, a
solvent such as those sold by Shell companies under the trade mark
"SHELLSOL", a polar solvent such as an ester and, in particular, an
alcohol, e.g. hexanol, 2-ethylhexanol, decanol, isotridecanol and
alcohol mixtures such as those sold by Shell companies under the
trade mark "LINEVOL", especially LINEVOL 79 alcohol which is a
mixture of C.sub.7-9 primary alcohols, or a C.sub.12-14 alcohol
mixture which is commercially available.
[0309] The total content of the additives in the diesel fuel
composition may be suitably between 0 and 10000 ppmw and preferably
below 5000 ppmw.
[0310] In the above, amounts (concentrations, % vol, ppmw, % wt) of
components are of active matter, i.e. exclusive of volatile
solvents/diluent materials.
[0311] The liquid fuel composition of the present invention is
produced by admixing the at least one essential fuel additive with
a base fuel suitable for use in an internal combustion engine. If
the base fuel to which the essential fuel additive is admixed is a
gasoline, then the liquid fuel composition produced is a gasoline
composition; likewise, if the base fuel to which the fuel additive
is admixed is a diesel fuel, then the liquid fuel composition
produced is a diesel fuel composition.
[0312] It has surprisingly been found that the use of a fuel
additive having a kinematic viscosity at 100.degree. C. of 27 cSt
or less and a NOACK volatility at 250.degree. C. of 100% wt,
preferably 20 wt % or less, and a friction modifier in liquid fuel
compositions provides benefits in terms of improved fuel economy of
an internal combustion engine being fuelled by the liquid fuel
composition containing said additive, in particular when the liquid
fuel composition of the present invention is a gasoline
composition, relative to the internal combustion engine being
fuelled by the liquid base fuel.
[0313] The present invention therefore provides a method of
improving the fuel economy performance of a liquid base fuel
suitable for use in an internal combustion engine, comprising
admixing at least one fuel additive having a kinematic viscosity at
100.degree. C. of 27 cSt or less and a NOACK volatility at
250.degree. C. of 100% wt, preferably 20 wt % or less, and at least
one friction modifier with a major portion of a liquid base fuel
suitable for use in an internal combustion engine.
[0314] Additionally, the use of the at least one fuel additive
having a kinematic viscosity at 100.degree. C. of 27 cSt or less
and a NOACK volatility at 250.degree. C. of 100% wt, preferably 20
wt % or less, in combination with a friction modifier in liquid
fuel compositions can also provide benefits in terms improving the
lubricant performance of an internal combustion engine being
fuelled by the liquid fuel composition of the present invention
relative to the internal combustion engine being fuelled by the
liquid base fuel.
[0315] Therefore, the present invention also provides a method of
improving the performance of the lubricant of an internal
combustion engine, said method comprising fuelling an internal
combustion engine containing the engine lubricant with a liquid
fuel composition according to the present invention.
[0316] Additionally, the use of the at least one fuel additive
having a kinematic viscosity at 100.degree. C. of 27 cSt or less
and a NOACK volatility at 250.degree. C. of 100% wt, preferably 20
wt % or less, and at least one friction modifier in liquid fuel
compositions can also provide benefits in terms of improving the
fuel economy performance of a lubricant of an internal combustion
engine being fuelled by the liquid fuel composition of the present
invention.
[0317] Therefore, the present invention provides a method of
improving the fuel economy performance of a lubricant of an
internal combustion engine, said method comprising fuelling the
internal combustion engine containing the lubricant with a liquid
fuel composition comprising: [0318] a base fuel suitable for use in
an internal combustion engine; and [0319] at least one fuel
additive having: [0320] (i) a kinematic viscosity at 100.degree. C.
of 27 cSt or less; and [0321] (ii) a NOACK volatility at
250.degree. C. of 100% wt, preferably 20% wt or less; and [0322] at
least one friction modifier.
Lubricating Oil
[0323] Lubricating oil compositions according to the present
invention contain a lubricating oil as the base fluid, and are
suitable for use as an engine crank case lubricant.
[0324] The total amount of lubricating oil incorporated in the
lubricating oil composition is at least 60 percent by weight,
preferably in the range of from 60 to 92 percent by weight, more
preferably in the range of from 75 to 90 percent by weight and most
preferably in the range of from 75 to 88 percent by weight, with
respect to the total weight of the lubricating oil composition.
[0325] There are no particular limitations regarding the
lubricating oil used in the lubricating oil composition, and
various conventional known mineral oils and synthetic oils may be
conveniently used.
[0326] The lubricating oil used in the lubricating oil composition
may conveniently comprise mixtures of one or more mineral oils
and/or one or more synthetic oils.
[0327] Mineral oils include liquid petroleum oils and
solvent-treated or acid-treated mineral lubricating oil of the
paraffinic, naphthenic, or mixed paraffinic/naphthenic type which
may be further refined by hydrofinishing processes and/or
dewaxing.
[0328] Naphthenic lubricating oils have low viscosity index (VI)
(generally 40-80) and a low pour point. Such lubricating oils are
produced from feedstocks rich in naphthenes and low in wax content
and are used mainly for lubricants in which colour and colour
stability are important, and VI and oxidation stability are of
secondary importance.
[0329] Paraffinic lubricating oils have higher VI (generally
>95) and a high pour point. Said lubricating oils are produced
from feedstocks rich in paraffins, and are used for lubricants in
which VI and oxidation stability are important.
[0330] Fischer-Tropsch derived lubricating oils may be conveniently
used in the lubricating oil composition, for example, the
Fischer-Tropsch derived lubricating oils disclosed in EP-A-776959,
EP-A-668342, WO-A-97/21788, WO-00/15736, WO-00/14188, WO-00/14187,
WO-00/14183, WO-00/14179, WO-00/08115, WO-99/41332, EP-1029029,
WO-01/18156 and WO-01/57166.
[0331] Synthetic processes enable molecules to be built from
simpler substances or to have their structures modified to give the
precise properties required.
[0332] Synthetic lubricating oils include hydrocarbon oils such as
olefin oligomers (PAOs), dibasic acids esters, polyol esters, and
dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the
Royal Dutch/Shell Group of Companies under the designation "XHVI"
(trade mark) may be conveniently used.
[0333] Preferably, the lubricating oil is constituted from mineral
oils and/or synthetic oils which contain more than 80% wt of
saturates, preferably more than 90 percent by weight, as measured
according to ASTM D2007.
[0334] It is further preferred that the lubricating oil contains
less than 1.0 percent by weight, preferably less than 0.1 percent
by weight of sulphur, calculated as elemental sulphur and measured
according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.
[0335] Preferably, the viscosity index of the lubricating oil, is
more than 80, more preferably more than 120, as measured according
to ASTM D2270.
[0336] Preferably, the lubricating oil has a kinematic viscosity in
the range of from 2 to 80 mm.sup.2/s at 100.degree. C., more
preferably in the range of from 3 to 70 mm.sup.2/s, most preferably
in the range of from 4 to 50 mm.sup.2/s.
[0337] The total amount of phosphorus in the lubricating oil is
preferably in the range of from 0.04 to 0.1 percent by weight, more
preferably in the range of from 0.04 to 0.09 percent by weight and
most preferably in the range of from 0.045 to 0.09 percent by
weight, based on total weight of the lubricating oil.
[0338] The lubricating oil preferably has a sulphated ash content
of not greater than 1.0 percent by weight, more preferably not
greater than 0.75 percent by weight and most preferably not greater
than 0.7 percent by weight, based on the total weight of the
lubricating oil.
[0339] The lubricating oil composition preferably has a sulphur
content of not greater than 1.2 percent by weight, more preferably
not greater than 0.8 percent by weight and most preferably not
greater than 0.2 percent by weight, based on the total weight of
the lubricating oil lubricating oil composition.
[0340] The lubricating oil composition may further comprise
additives such as anti-oxidants, anti-wear additives, detergents,
dispersants, friction modifiers, viscosity index improvers, pour
point depressants, corrosion inhibitors, defoaming agents and seal
fix or seal compatibility agents.
[0341] Antioxidants that may be conveniently used include those
selected from the group of aminic antioxidants and/or phenolic
antioxidants.
[0342] In a preferred embodiment, said antioxidants are present in
an amount in the range of from 0.1 to 5.0 percent by weight, more
preferably in an amount in the range of from 0.3 to 3.0 percent by
weight, and most preferably in an amount of in the range of from
0.5 to 1.5 percent by weight, based on the total weight of the
lubricating oil composition.
[0343] The lubricating oil composition may conveniently contain a
single zinc dithiophosphate or a combination of two or more zinc
dithiophosphates as anti-wear additives, the or each zinc
dithiophosphate being selected from zinc dialkyl-, diaryl- or
alkylaryl-dithiophosphates.
[0344] The lubricating oil composition may generally contain in the
range of from 0.4 to 1.0 percent by weight of zinc dithiophosphate,
based on total weight of the lubricating oil composition.
[0345] Additional or alternative anti-wear additives may be
conveniently used in the lubricating oil composition of the present
invention.
[0346] Suitable alternative anti-wear additives include
boron-containing compounds such as borate esters, borated fatty
amines, borated epoxides, alkali metal (or mixed alkali or alkaline
earth metal) borates and borated overbased metal salts. Said
boron-containing anti-wear additives may be conveniently added to
the lubricating oil in an amount in the range of from 0.1 to 3.0
percent by weight, based on the total weight of lubricating oil
composition.
[0347] Typical detergents that may be used in the lubricating oil
composition include one or more salicylate and/or phenate and/or
sulphonate detergents.
[0348] However, as metal organic and inorganic base salts which are
used as detergents can contribute to the sulphated ash content of a
lubricating oil composition, in a preferred embodiment of the
present invention, the amounts of such additives are minimised.
[0349] Furthermore, in order to maintain a low sulphur level,
salicylate detergents are preferred.
[0350] Thus, in a preferred embodiment, the lubricating oil
composition may contain one or more salicylate detergents.
[0351] In order to maintain the total sulphated ash content of the
lubricating oil composition at a level of preferably not greater
than 1.0 percent by weight, more preferably at a level of not
greater than 0.75 percent by weight and most preferably at a level
of not greater than 0.7 percent by weight, based on the total
weight of the lubricating oil composition, said detergents are
preferably used in amounts in the range of 0.05 to 12.5 percent by
weight, more preferably from 1.0 to 9.0 percent by weight and most
preferably in the range of from 2.0 to 5.0 percent by weight, based
on the total weight of the lubricating oil composition.
[0352] Furthermore, it is preferred that said detergents,
independently, have a TBN (total base number) value in the range of
from 10 to 500 mg.KOH/g, more preferably in the range of from 30 to
350 mg.KOH/g and most preferably in the range of from 50 to 300
mg.KOH/g, as measured by ISO 3771.
[0353] The lubricating oil compositions may additionally contain an
ash-free dispersant which is preferably admixed in an amount in the
range of from 5 to 15 percent by weight, based on the total weight
of the lubricating oil composition.
[0354] Examples of ash-free dispersants which may be used include
the polyalkenyl succinimides and polyalkenyl succininic acid esters
disclosed in Japanese Patent Nos. 1367796, 1667140, 1302811 and
1743435. Preferred dispersants include borated succinimides.
[0355] Examples of viscosity index improvers which may conveniently
used in the lubricating oil composition include the
styrene-butadiene copolymers, styrene-isoprene stellate copolymers
and the polymethacrylate copolymer and ethylene-propylene
copolymers. Such viscosity index improvers may be conveniently
employed in an amount in the range of from 1 to 20 percent by
weight, based on the total weight of the lubricating oil
composition.
[0356] Polymethacrylates may be conveniently employed in the
lubricating oil compositions as effective pour point
depressants.
[0357] Furthermore, compounds such as alkenyl succinic acid or
ester moieties thereof, benzotriazole-based compounds and
thiodiazole-based compounds may be conveniently used in the
lubricating oil composition as corrosion inhibitors.
[0358] Compounds such as polysiloxanes, dimethyl polycyclohexane
and polyacrylates may be conveniently used in the lubricating oil
composition as defoaming agents.
[0359] Compounds which may be conveniently used in the lubricating
oil composition as seal fix or seal compatibility agents include,
for example, commercially available aromatic esters.
[0360] The present invention will be further understood from the
following examples. Unless otherwise stated, all amounts and
concentrations disclosed in the examples are based on weight of the
fully formulated fuel composition.
EXAMPLES
Example 1
[0361] In the following example, three commercially available
friction modifiers (FM) were used:
[0362] FM10--this is a reaction product of oleic acid and
aminoethylethanolamine having a 3:1 molar ratio as per Example 4 of
WO2009/50287.
[0363] FM11--this is the reaction products of C.sub.8-C.sub.18
fatty acids and C18 unsaturated fatty acids with diethanolamine and
propylene oxide (as disclosed in WO2010/05720).
[0364] FM14--CH-5 commercially available from Sanzheng Polymer
Company.
[0365] In the following example, a commercially available viscosity
control agent (VCA) was used as follows:
[0366] VCA2--Synfluid PAO-5 commercially available from
Chevron.
[0367] Table 1 shows the relative amounts (in wt %) of the various
additives (detergent additive package, VCA, FM and solvent) present
in each of the additive blends.
[0368] In some examples, a solvent eg Shellsol A150 commercially
available from Shell and 2-ethylhexanol is also blended into the
additive package to improve stability and handling of the additive
package.
TABLE-US-00001 TABLE 1 1 2 3 4 5 6 Detergent 46.0 85.5 42.4 74.1
85.5 74.1 Additive package FM10 6.9 0 6.4 0 0 0 FM11 0 12.8 0 11.1
0 0 FM14 0 0 0 0 12.8 11.1 VCA2 0.9 1.7 8.5 14.8 1.7 14.8 Solvent
46.2 0 42.7 0 0 0 Total 100 100 100 100 100 100 Kv40.sup.1 6.676
30.14 7.073 29.14 n.d. n.d. Kv100.sup.2 2.083 6.118 2.173 5.948
n.d. n.d. .sup.1Kinematic Viscosity at 40.degree. C. in mm.sup.2/s
according to standard test method IP 71 (Energy Institute UK) which
corresponds to ASTM D 445 .sup.2Kinematic Viscosity at 100.degree.
C. in mm.sup.2/s according to standard test method IP 71 (Energy
Institute UK) which corresponds to ASTM D 445 n.d. = not
determined
[0369] The additive blends shown in Table 1 have improved
handlability properties such as improved viscosity
characteristics.
[0370] The additive blends from Table 1 are each blended into an
EN228 gasoline fuel in an amount of 10 to 6000 ppmw, based on the
total gasoline fuel composition.
[0371] The fuel compositions of the examples provide improved fuel
economy benefits, good cleaniness and reduced friction by both
hydrodynamic and boundary lubrication effects.
Examples 2 to 5
[0372] The composition and properties of a number of commercially
available components that can be used as first fuel additive and
second fuel additive are given below. Certain of these components
are used in Examples 2 to 5.
[0373] Durasyn 165, a PAO-5 commercially available from INEOS
Oligomers.
[0374] Durasyn 162, a PAO-2 commercially available from INEOS
Oligomers.
[0375] Priolube 3970, a C7-C9 ester of trimethylolpropane
commercially available from Croda Europe Limited.
[0376] FM10--this is a reaction product of oleic acid and
aminoethylethanolamine having a 3:1 molar ratio as per Example 4 of
WO2009/50287.
[0377] Ethomeen T12e, an ethoxylated amine produced from
tallowamine with an average 2 moles of ethyleneoxide, commercially
available from AkzoNobel.
[0378] FM11--this is the reaction product of C8-C18 fatty acids and
C18 unsaturated fatty acids with diethanolamine and propylene oxide
(as disclosed in WO2010/05720).
TABLE-US-00002 KV NOACK 100.degree. C. 250.degree. C. ASTM ASTM
D445 D5800 Trade Name Supplier Chemistry (cSt) (% wt) Durasyn 162
INEOS Poly Alpha 2.1 99 Oligomers Olefin 2 Durasyn 164 INEOS Poly
Alpha 4.1 14 Oligomers Olefin 4 Durasyn 166 INEOS Poly Alpha 6.1 9
Oligomers Olefin 6 Durasyn 168 INEOS Poly Alpha 7.77 3.13 Oligomers
Olefin 8 Synfluid PAO 5 Chevron Poly Alpha 5.1 5.8 Corporation
Olefin 5 Durasyn 165 INEOS Poly Alpha 5.1 5.5 Oligomers Olefin 5
Durasyn 125 INEOS Poly Alpha 5.1 5.5 Oligomers Olefin 5 Priolube
3970 Croda TMP Cocoate 4.4 4.5 Europe Ester Limited Priolube1858
Croda Diisodecyl 4.5 7.2 Europe Azelate Limited Ester Synative ES
EHO Cognis Gmbh 2- 2.8 20 Ethylhexyl Oleate Ester Synative ES 3824
Cognis Gmbh Neopentyl 2.5 7.6 Glycol Cocoate/C8-10 Ester
Example 2
[0379] Products 1-18 were tested using a modified HFRR (ISO 12156)
method to allow testing in gasoline. The lubricity of the gasoline
compositions was determined by using a modified HFRR test. The
modified HFRR test is based on ISO 12156-1 using a PCS Instruments
HFRR supplemented with the PCS Instruments Gasoline Conversion Kit,
and using a fluid volume of 15.0 ml (+/-0.2 ml), a fluid
temperature of 25.0.degree. C. (+/-1.degree. C.), and wherein a
PTFE cover is used to cover the test sample in order to minimise
evaporation.
[0380] The additives were tested at 200 mg/L in an unleaded
gasoline meeting EN228 specifications, containing no ethanol (E0).
Lower lubricity and friction coefficient results are indications of
better friction modification effects and indicates better fuel
economy. This is shown by Friction modifiers d to j in Table 2
below.
TABLE-US-00003 TABLE 2 Lubricity result Friction (microns)
Coefficient Test molecule average average Base Fuel Unleaded
gasoline 872.5 0.641 ULG95, E0 Detergent a PIB Succinimide 720
0.448 (type A8) detergent Detergent b Poly ether amine 887 0.632
(type A6) detergent Detergent c PIBAmine 871 0.812 (type A1)
detergent Friction FM11 534.5 0.284 modifier d Friction Kerocom
K3561 385.5 0.212 modifier e Friction FM10 401 0.246 modifier f
Friction Ultrazol 9525 549.5 0.281 modifier g Friction Priolube
1407 308 0.196 modifier h Friction Ethomeen T12e 481 0.287 modifier
i Friction Ethomeen O15 697 0.344 modifier j VCA k PAO 2 (Durasyn
879.5 0.683 162) VCA l PAO 4 (Durasyn 872.5 0.657 164) VCA m PAO 5
(Synfluid 880.5 0.729 PAO 5) VCA n PAO 8 (Durasyn 870.5 0.668 168)
VCA o Priolube 3970 890 0.717 VCA p Synative ES 3824 869 0.636 VCA
q Priolube1858 844 0.771 VCA r SYNATIVE ES EHO 857 0.636
[0381] This example shows that molecules designed for detergent
performance (a-c) do not show friction modification performance,
and molecules designed for VCA performance (k-r) do not show
friction modification performance.
Example 3
[0382] 3 vehicles of Five models (see Table 3) completed 10,000
miles of on-road mixed driving style mileage accumulation. The
vehicles used standard ULG95, an ethanol-free base fuel that meets
standard specification EN 228. In each case the base fuel was
pre-treated with the same commercial detergent additive package,
and each fuel additionally contained a test additive at a
concentration detailed in Table 4.
TABLE-US-00004 TABLE 3 VW Golf 1.6 ltr S Ford Mondeo 2.0 ltr Edge
Mitsubishi Lancer 1.8 ltr GS2 GM Zafira 1.6 16 v Active Honda Civic
1.8 SE
TABLE-US-00005 TABLE 4 Test Fuel Composition (Test) Fuel (Test)
Fuel (Test) Fuel Base Fuel EN228 ULG95 EN228 ULG95 EN228 ULG95
Lubricant Shell Helix Shell Helix Shell Helix HX7 SAE 10W- HX7 SAE
5W- HX7 SAE 5W- 40 30 30 Detergent Commercial Commercial Commercial
Package Package Package Package Test Additives PAO5 at CH-2C at
CH-5 at 1000 ppmw 200 ppmw 200 ppmw Average Test 6.1% m/m 1.6% m/m
1.6% m/m Additive concentration in lubricant after 10,000 miles
Average fuel 0.74% 0.84% 0.54% economy (steady state) benefit
across 5 models
[0383] Fuel consumption was measured at steady state conditions (32
km/h 2.sup.nd gear). Duplicate emissions tests were carried out on
each vehicle at 10,000 miles.
[0384] Test additive concentration in the lubricant after 10,000
miles was determined by either GC--gas chromatography (PAO5) or NMR
(CH-2C and CH-5).
[0385] Friction modifiers CH-2C and CH-5 are commercially available
from Shanghai Sanzheng Polymer Company.
[0386] PAO-5 is Synfluid PAO 5 commercially available from Chevron
Philips.
Example 4
[0387] Two fuels were tested to study additive transfer into a
lubricant.
[0388] A test was run on a pair of Ford Focus ST-2 2.51tr cars with
about 22,000 miles on the odometer. The lubricant used was Helix
Ultra Extra 5W-30 commercially available from Shell Lubricants. The
base fuel was an EN228 gasoline base fuel. The cars were run on
additised fuel containing detergent package, friction modifier and
viscosity control additive.
[0389] The lubricant was sampled at the start of test and end of a
12,000 mile accumulation on a high speed cycle chassis dynameter
programme. No oil top ups were permitted. The amount of additive in
the lubricant, at the start and accumulated by the end of test, was
measured by GC for the POA5 and Priolube 3970 or LC-MS (liquid
chromatography--mass spectrometry) for FM10.
TABLE-US-00006 TABLE 5 Increase in Increase in Concentration
Concentration Friction Concentration in lubricant Viscosity
Concentration in lubricant Test modifier in fuel after test control
additive in fuel after test 1 FM10 225 ppmw 2000 ppmw Synfluid POA5
1000 ppmw 4.5% m/m 2 FM10 225 ppmw 2100 ppmw Priolube3970 1000 ppmw
5.1% m/m
[0390] Examples 3 and 4 confirm that both friction modifiers and
VCA chemistry can be transferred from the fuel to the lubricant,
and, from Example 3, provide fuel economy benefits.
Example 5
[0391] The fuel consumption and fuel economy benefit of various
additives dosed directly into the lubricant in the engine sump to
mimic the accumulation of additives and additive combinations, as
shown to occur in Example 4, was compared with that of an undosed
lubricant by using a bench engine test. The test used a Ford Zetec
1.988 litre 4-cylinder inline DOHC petrol engine. The fuel used was
an EN228 Low Sulphur E5 Gasoline. The lubricant used was Shell
Helix 5W-30 or Shell Helix Plus 10W40.
[0392] The engine was clean and free from abnormal levels of Inlet
Valve Deposits (IVDs) and Combustion Chamber Deposits (CCDs). The
test was based on the continuous repetition of the set of
speed/load points (test cycle). The cycle was repeated over a total
period of approximately 21 hours (16 hours overnight lubricant
de-greening and 5 hours fuel consumption measurements) with
scheduled breaks for the acquisition of lubricant samples and the
injection of the additive into the crankcase. The percentage change
in the brake specific fuel consumption (BSFC) measurement between
pre and post sump dosing are shown in the Table below with the data
expressed as an average of the test conditions for ease of
comparison.
TABLE-US-00007 TABLE 6 Test Concentration Average BSFC A NULL
-0.03% B CH-5 1% v 0.86% C CH-5 2% v 1.36% D CH-5 4% v 1.24% E
CH-2C 2% v 0.27% F CH-6 2% v 0.15% G Ethomeen T12e 2% v 1.19% H
Keracom 3561 2% v 1.36% I FM10 2% v 1.23% J Synfluid PAO-5 2% v
0.34% K Ethomeen T12e 2% v 1.36% L PAO2 (Durasyn 162) 10% v 0.48% M
Ethomeen T12e + PAO2 Ethomeen T12e 2.17% (Durasyn 162) (2% v) +
PAO2 (10% v) N Ethomeen T12e 2% v 1.57% O Ethomeen O15 2% v 1.24% P
FM10 + Synfluid PAO5 FM10 (2% v) + 1.29% PAO5 (10% v) Q FM10 +
Priolube 3970 FM10 (2% v) + 1.31% Priolube 3970(10% v) R Ethomeen
O15 + Ethomeen O15 1.26% Synfluid PAO5 (2% v) + PAO5 (10% v)
[0393] This example confirms that both friction modifiers and VCA
chemistry can cause an increase in % benefit fuel consumption when
present in the lubricant. A combination of both friction modifiers
and VCA components show an increase in % benefit in fuel
consumption over and above an additive increase.
[0394] The combined results of Examples 3 and 5 show the benefit of
using both friction modifiers and VCA in fuel additive formulations
to improve fuel consumption, i.e. to improve fuel economy.
* * * * *