U.S. patent application number 15/553217 was filed with the patent office on 2018-02-08 for use of a lubricating composition.
The applicant listed for this patent is SHELL OIL COMPANY. Invention is credited to Neal Matthew MORGAN, Caroline Nicola ORLEBAR, Mark Clift SOUTHBY.
Application Number | 20180037838 15/553217 |
Document ID | / |
Family ID | 52595156 |
Filed Date | 2018-02-08 |
United States Patent
Application |
20180037838 |
Kind Code |
A1 |
ORLEBAR; Caroline Nicola ;
et al. |
February 8, 2018 |
USE OF A LUBRICATING COMPOSITION
Abstract
The present invention relates to a method for advancing the
spark timing of a spark-ignited internal combustion engine, the
method comprising lubricating the spark-ignited internal combustion
engine with a lubricating composition comprising base oil and an
anti-knock additive, wherein the anti-knock additive is an aromatic
amine.
Inventors: |
ORLEBAR; Caroline Nicola;
(London, GB) ; MORGAN; Neal Matthew; (Knutsford,
Cheshire, GB) ; SOUTHBY; Mark Clift; (London,
GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHELL OIL COMPANY |
HOUSTON |
TX |
US |
|
|
Family ID: |
52595156 |
Appl. No.: |
15/553217 |
Filed: |
February 18, 2016 |
PCT Filed: |
February 18, 2016 |
PCT NO: |
PCT/EP2016/053443 |
371 Date: |
August 24, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2040/255 20200501;
C10M 133/12 20130101; C10M 2215/062 20130101; C10M 2215/06
20130101; C10M 2215/064 20130101; C10M 2215/066 20130101; C10M
2215/221 20130101; C10N 2030/00 20130101; C10N 2030/54 20200501;
C10M 2215/223 20130101 |
International
Class: |
C10M 133/12 20060101
C10M133/12 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 27, 2015 |
EP |
15157005.8 |
Claims
1. (canceled)
2. (canceled)
3. (canceled)
4. (canceled)
5. (canceled)
6. A method for advancing the spark timing of a spark-ignited
internal combustion engine, the method comprising lubricating the
spark-ignited internal combustion engine with a lubricating
composition comprising base oil and an anti-knock additive, wherein
the anti-knock additive is an aromatic amine.
7. (canceled)
8. (canceled)
9. The method according to claim 6, wherein the lubricating
composition comprises from 3 to 20 wt % of the aromatic amine.
10. A method for advancing the spark timing of a spark-ignited
internal combustion engine, the method comprising a step of adding
an anti-knock additive to the lubricating composition used to
lubricate the spark-ignited internal combustion engine, wherein the
anti-knock additive is an aromatic amine.
11. (canceled)
12. (canceled)
13. The method according to claim 10, wherein the step of adding an
anti-knock additive to the lubricating composition comprises (i)
fuelling the spark-ignited internal combustion engine with a fuel
composition comprising a base fuel and an anti-knock additive,
wherein the anti-knock additive is an aromatic amine, and (ii)
transfer of anti-knock additive during operation of the engine from
the fuel composition to the lubricating composition.
14. The method according to claim 10, wherein the aromatic amine is
selected from aniline and alkyl-substituted aniline compounds,
1,2,3,4-tetrahydroquinoline, diphenylamine and alkyl-substituted
diphenylamine compounds, 2-ethylhexyl-4-(dimethylamino)benzoate,
indoline, N,N-dimethyl-1,4-phenylenediamine, o-toluidine,
p-toluidine, p-anisidine, p-phenetidine, and mixtures thereof.
15. The method according to claim 6, wherein the aromatic amine is
selected from aniline and alkyl-substituted aniline compounds,
1,2,3,4-tetrahydroquinoline, diphenylamine and alkyl-substituted
diphenylamine compounds, 2-ethylhexyl-4-(dimethylamino)benzoate,
indoline, N,N-dimethyl-1,4-phenylenediamine, o-toluidine,
p-toluidine, p-anisidine, p-phenetidine, and mixtures thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the use of a lubricating
composition for providing spark timing advance of a spark-ignited
internal combustion engine. The present invention further relates
to a method for advancing the spark timing of a spark-ignition
internal combustion engine.
BACKGROUND OF THE INVENTION
[0002] Under ideal conditions, normal combustion in a conventional
spark-ignition internal combustion engine occurs when a mixture of
fuel and air is ignited within the combustion chamber inside the
cylinder by the production of a spark originating from a spark
plug. Such normal combustion is generally characterised by the
expansion of the flame front across the combustion chamber in an
orderly and controlled manner.
[0003] Ignition timing in a spark-ignition internal combustion
engine is the process of setting the angle relative to piston
position and crankshaft angular velocity that a spark will occur in
the combustion chamber near the end of the compression stroke.
[0004] The engine needs to fire the spark in advance of top dead
centre because fuel does not burn completely the instant the spark
fires, the combustion gases take a period of time to expand, and
the angular or rotational speed of the engine can lengthen or
shorten the time frame in which the burning and expansion should
occur. In a vast majority of cases, the angle will be described as
a certain angle advanced before top dead centre (BTDC). Advancing
the spark BTDC means that the spark is energised prior to the point
where the combustion chamber reaches its minimum size, since the
purpose of the power stroke in the engine is to force the
combustion chamber to expand. Sparks occurring after top dead
center (ATDC) are usually counter-productive (producing wasted
spark, back-fire, engine knock, etc.) unless there is need for a
supplemental or continuing spark prior to the exhaust stroke.
[0005] Setting the correct ignition timing is crucial in the
performance of an engine. Sparks occurring too soon or too late in
the engine cycle are responsible for excessive vibrations and even
engine damage. The ignition timing affects many variables including
engine longevity, fuel economy, and engine power. Modern engines
that are controlled in real time by an engine control unit (ECU)
use a computer to control the timing throughout the engine's RPM
and load range.
[0006] There are many factors that influence proper ignition timing
for a given engine. These include the timing of the intake valve(s)
or fuel injector(s), the type of ignition system used, the type and
condition of the spark plugs, the contents and impurities of the
fuel, fuel temperature and pressure, engine speed and load, air and
engine temperature, turbo boost pressure or intake air pressure,
the components used in the ignition system, and the settings of the
ignition system components. Usually, any major engine changes or
upgrades will require a change to the ignition timing settings of
the engine.
[0007] The present inventors have now found that by adding certain
anti-knock additives to the sump, in particular by adding
anti-knock additives having an aromatic amine structure, benefits
can be achieved in terms of advanced spark timing.
[0008] WO2004/101717 relates to a lubricant composition for
reducing the propensity of end gas knock in a flame propagation
engine comprising a base oil and one or more additives that
increases the octane of the composition. Examples of additives
mentioned in WO2004/101717 which can be used as an octane booster
include alcohols, ethers, esters and organometallic compounds.
Aromatic amines are not mentioned in WO2004/101717 as octane
boosters.
SUMMARY OF THE INVENTION
[0009] According to a first aspect of the present invention there
is provided the use of an anti-knock additive in a lubricating
composition for providing spark timing advance of a spark-ignition
internal combustion engine, wherein the anti-knock additive is an
aromatic amine.
[0010] According to another aspect of the present invention there
is provided the use of an anti-knock additive in a lubricating
composition for reducing the fuel flow requirement of a
spark-ignition internal combustion, wherein the anti-knock additive
is an aromatic amine.
[0011] According to a further aspect of the present invention there
is provided the use of an anti-knock additive in a lubricating
composition for reducing the brake specific fuel consumption of a
spark-ignition internal combustion engine.
[0012] According to a further aspect of the present invention there
is provided a method for advancing the spark timing of a
spark-ignition internal combustion engine, the method comprising
lubricating the spark-ignition internal combustion engine with a
lubricating composition comprising base oil and anti-knock
additive, wherein the anti-knock additive is an aromatic amine.
[0013] According to a further aspect of the present invention there
is provided a method for reducing the fuel flow requirement of a
spark-ignition internal combustion engine, the method comprising
lubricating the engine with a lubricating composition comprising
base oil and anti-knock additive, wherein the anti-knock additive
is an aromatic amine.
[0014] According to a further aspect of the present invention there
is provided a method for reducing the brake specific fuel
consumption of a spark-ignition internal combustion engine, the
method comprising lubricating the engine with a lubricating
composition comprising base oil and anti-knock additive, wherein
the anti-knock additive is an aromatic amine.
[0015] According to a further aspect of the present invention there
is provided a method for advancing the spark timing of a
spark-ignition internal combustion engine, the method comprising
lubricating the engine with a lubricating composition, wherein the
method further comprises a step of adding an anti-knock additive to
the lubricating composition, wherein the anti-knock additive is an
aromatic amine.
[0016] According to a further aspect of the present invention there
is provided a method for reducing the fuel flow requirement of a
spark-ignition internal combustion engine, the method comprising
lubricating the engine with a lubricating composition, wherein the
method further comprises a step of adding an anti-knock additive to
the lubricating composition, wherein the anti-knock additive is an
aromatic amine.
[0017] According to a further aspect of the present invention there
is provided a method for reducing the brake specific fuel
consumption of a spark-ignition internal combustion engine, the
method comprising a step of adding an anti-knock additive to the
lubricating composition, wherein the anti-knock additive is an
aromatic amine.
[0018] The features and advantages of the present invention will be
apparent to those skilled in the art. While numerous changes may be
made by those skilled in the art, such changes are within the
spirit of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0019] As used herein the term "spark timing" means the process of
setting the angle relative to piston position and crankshaft
angular velocity in a spark-ignition internal combustion engine so
that a spark will occur in the combustion chamber near the end of
the compression stroke.
[0020] As used herein the term "advancing the spark timing" means
bringing the spark earlier than the current or base calibration for
the particular speed/load conditions, while minimising the chance
of, and preferably avoiding, knocking.
[0021] The methods and uses of lubricant compositions herein may be
used to achieve any amount of advancement of the spark timing of
the engine, while minimising the chance of, and preferably
avoiding, knocking. It may be used for the purpose of achieving a
desired target level of spark timing. The present invention
preferably achieves a 0.1 CAD advancement or more in the spark
timing of the engine, more preferably a 0.5 CAD advancement or more
in the spark timing of the engine, even more preferably a 5 CAD
advancement or more in the spark timing of the engine, and
especially a 10 CAD advancement or more in the spark timing of the
engine.
[0022] As used herein the term "fuel flow requirement" means the
mass of fuel consumed by the spark-ignition internal combustion
engine per hour in endeavouring to meet the demands of the
driver.
[0023] As used herein the term "reducing the fuel flow requirement"
means reducing the mass of fuel consumed by the spark-ignition
internal combustion engine per hour in endeavouring to meet the
demands of the driver. The methods, uses and lubricating
compositions of the present invention provide the same power from
less fuel due to the efficient way the engine is consuming the
fuel.
[0024] The methods and uses of lubricating compositions of the
present invention may be used to achieve any amount of reduction in
the fuel flow requirement of the engine. The present invention may
be used for the purpose of achieving a desired target level of fuel
flow requirement. The methods and uses of lubricating compositions
of the present invention preferably achieve a 0.5% reduction or
more in the fuel flow requirement of the engine, more preferably a
1% reduction or more in the fuel flow requirement of the engine,
even more preferably a 5% reduction or more in the fuel flow
requirement of the engine, and especially a 10% reduction or more
in the fuel flow requirement of the engine.
[0025] As used herein the term "brake specific fuel consumption"
means the rate of fuel consumption divided by the power produced by
the engine.
[0026] As used herein the term "reducing the brake specific fuel
consumption" means reducing the rate of fuel consumption divided by
the power produced by the engine.
[0027] The methods and uses of lubricant compositions herein may be
used to achieve any amount of reduction in the brake specific fuel
consumption of the engine. The present invention may be used for
the purpose of achieving a desired target level of brake specific
fuel consumption. The method and use herein preferably achieves a
0.5% reduction or more in the brake specific fuel consumption of
the engine, more preferably a 1% reduction or more in the brake
specific fuel consumption of the engine, even more preferably a 5%
reduction or more in the brake specific fuel consumption of the
engine, and especially a 10% reduction or more in the brake
specific fuel consumption of the engine.
[0028] A first essential component of the lubricating composition
used in the present invention is an anti-knock additive. The
anti-knock additive used in the present invention is an aromatic
amine.
[0029] Any aromatic amine suitable for use as an anti-knock
additive in a lubricating composition or a fuel composition for a
spark-ignition internal combustion engine can be used herein.
[0030] Suitable aromatic amine compounds for use herein include
aniline and alkyl-substituted aniline compounds,
1,2,3,4-tetrahydroquinoline, diphenylamine and alkyl-substituted
diphenylamine compounds such as butyldiphenylamine,
octyldiphenylamine and di-octyl-diphenylamine,
2-ethylhexyl-4-(dimethylamino)benzoate, indoline,
N,N-dimethyl-1,4-phenylenediamine, o-toluidine, p-toluidine,
p-anisidine, p-phenetidine, and the like, and mixtures thereof.
[0031] Suitable alkyl-substituted aniline compounds for use herein
include those compounds disclosed in WO2008/076759 incorporated
herein by reference.
[0032] Suitable alkyl-substituted aniline compounds for use herein
include those having the formula I below:
##STR00001##
wherein X is selected from --OR.sup.1 or --NR.sup.2R.sup.3, R.sup.1
and R.sup.2 are independently selected from methyl, ethyl, propyl,
butyl and tertiary-butyl, R.sup.3 is selected from hydrogen,
methyl, ethyl, propyl, butyl and tertiary-butyl, R.sup.4 is
selected from hydrogen, methyl, ethyl and propyl, R.sup.5 is
selected from hydrogen and C.sub.1-C.sub.4 straight or branched
chain alkyl groups.
[0033] Examples of alkyl-substituted aniline compounds for use
herein include p-methoxy aniline, p-N-methyl-1,4-diaminobenzene,
p-ethoxy aniline, (bis-N,N'-methyl)-1-4-diaminobenzene, p-n-propoxy
aniline, p-n-butoxy aniline, p-2-methyl-1-propoxy aniline,
p-N-dimethyl aniline, p-N-diethyl aniline, p-N-1-dipropyl aniline,
p-N-di-1-butyl aniline, p-N-di-2-methyl-1-propyl aniline,
p-methoxy-2,6-dimethyl aniline, p-methoxy-2,6-diethyl aniline,
p-methoxy-2,6-di-1-propyl aniline, p-methoxy-2,6-di-1-butyl
aniline, p-methoxy-2,6-di-2-methyl-1-propyl aniline,
p-ethoxy-2,6-dimethyl aniline, p-ethoxy-2,6-diethyl aniline,
p-ethoxy-2,6-di-1-propyl aniline, p-ethoxy-2,6-di-1-butyl aniline,
p-ethoxy-2,6-di-2-methyl-1-propyl aniline, p-N-dimethyl-N'-methyl
aniline, p-N-diethyl-N'-ethyl aniline,
p-N-dimethyl-2,6-dimethyl-N'-methyl aniline,
p-N-dimethyl-2,6-diethyl-N'-methyl aniline,
p-N-dimethyl-2,6-(1-propyl)-N'-methyl aniline,
p-N-dimethyl-2,6-(1-butyl)-N'-methyl aniline,
p-N-dimethyl-2,6-(2-methyl-1-propyl)-N'-methyl aniline,
p-N-diethyl-2,6-dimethyl-N'-methyl aniline,
p-N-diethyl-2,6-diethyl-N'-methyl aniline,
p-N-diethyl-2,6-(1-propyl)-N'-methyl aniline,
p-N-diethyl-2,6-(1-butyl)-N'-methyl aniline,
p-N-diethyl-2,6-(2-methyl-1-propyl)-N'-methyl aniline,
p-N-di-1-propyl-2,6-dimethyl-N'-methyl aniline,
p-N-di-1-propyl-2,6-diethyl-N'-methyl aniline,
p-N-di-1-propyl-2,6-(1-propyl)-N'-methyl aniline,
p-N-di-1-propyl-2,6-(1-butyl)-N'-methyl aniline,
p-N-di-1-propyl-2,6-(2-methyl-1-propyl)-N'-methyl aniline,
butylaniline, and N-methyl aniline.
[0034] Preferred aromatic amines for use herein are selected from
1,2,3,4-tetrahydroquinoline, alkyl-substituted anilines, and
mixtures thereof.
[0035] Particularly preferred aromatic amines for use herein are
selected from 1,2,3,4-tetrahydroquinoline and N-methyl aniline, and
mixtures thereof.
[0036] In one embodiment of the present invention, the aromatic
amine is an alkyl-substituted aniline, preferably N-methyl
aniline.
[0037] In another embodiment of the present invention, the aromatic
amine is an 1,2,3,4-tetrahydroquinoline.
[0038] In one embodiment of the present invention, the anti-knock
additive is present in the lubricating composition at a level of
from 0.01 to 20 wt %, preferably from 0.1 to 10 wt %, more
preferably from 1 to 10 wt %, even more preferably from 5 to 10 wt
%, by weight of the lubricating composition.
[0039] In another embodiment of the present invention, the
anti-knock additive is present in the lubricating composition at a
level of from 3 to 20 wt %, preferably from 5 to 20 wt %, more
preferably from 5 to 15 wt %, even more preferably from 10 to 15 wt
%, by weight of the lubricating composition.
[0040] The concentration of anti-knock additive referred to above
means the concentration of anti-knock additive which is added into
the lubricating composition as a blend with all the other
components of the lubricating composition, and does not include the
concentration of any other types of additives having an aromatic
amine structure, for example anti-oxidant additives, which may
already be present in the lubricating composition.
[0041] The lubricating composition further comprises base oil.
There are no particular limitations regarding the base oil(s) used
in lubricating composition according to the present invention, and
various conventional mineral oils, synthetic oils as well as
naturally derived esters such as vegetable oils may be conveniently
used. Any base oil which belongs to Group I, Group II, Group III,
Group IV, Group V and so on of the API (American Petroleum
Institute) base oil categories, may be conveniently used.
Furthermore, the base oil may conveniently comprise mixtures of one
or more mineral oils and/or one or more synthetic oils; thus, the
term "base oil" may refer to a mixture comprising more than one
base oil.
[0042] 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.
[0043] Naphthenic base oils have low viscosity index (VI)
(generally 40-80) and a low pour point. Such base 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.
[0044] Paraffinic base oils have higher VI (generally >95) and a
high pour point. Such base oils are produced from feedstocks rich
in paraffins, and are used for lubricants in which VI and oxidation
stability are important.
[0045] Synthetic oils include hydrocarbon oils such as olefin
oligomers (including polyalphaolefin base oils; PAOs),
Fischer-Tropsch derived base oils, dibasic acid esters, polyol
esters, polyalkylene glycols (PAGs), alkyl naphthalenes and dewaxed
waxy isomerates.
[0046] Fischer-Tropsch derived base oils are known in the art. By
the term "Fischer-Tropsch derived" is meant that a base oil is, or
is derived from, a synthesis product of a Fischer-Tropsch process.
A Fischer-Tropsch derived base oil may also be referred to as a GTL
(Gas-To-Liquids) base oil. Suitable Fischer-Tropsch derived base
oils that may be conveniently used as the base oil in the
lubricating composition of the present invention are those as for
example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO
00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO
00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO
01/57166.
[0047] Typically, the aromatics content of a Fischer-Tropsch
derived base oil, suitably determined by ASTM D 4629, will
typically be below 1 wt %, preferably below 0.5 wt % and more
preferably below 0.1 wt %. Suitably, the base oil has a total
paraffin content of at least 80 wt %, preferably at least 85, more
preferably at least 90, yet more preferably at least 95 and most
preferably at least 99 wt %. It suitably has a saturates content
(as measured by IP-368) of greater than 98 wt %. Preferably the
saturates content of the base oil is greater than 99 wt %, more
preferably greater than 99.5 wt %. It further preferably has a
maximum n-paraffin content of 0.5 wt %. The base oil preferably
also has a content of naphthenic compounds of from 0 to less than
20 wt %, more preferably of from 0.5 to 10 wt %.
[0048] Typically, the Fischer-Tropsch derived base oil or base oil
blend has a kinematic viscosity at 100.degree. C. (as measured by
ASTM D445) in the range of from 1 to 30 mm.sup.2/s (cSt),
preferably from 1 to 25 mm.sup.2/s (cSt), and more preferably from
2 mm.sup.2/s to 12 mm.sup.2/s. Preferably, the Fischer-Tropsch
derived base oil has a kinematic viscosity at 100.degree. C. (as
measured by ASTM D445) of at least 2.5 mm.sup.2/s, more preferably
at least 3.0 mm.sup.2/s. In one embodiment of the present
invention, the Fischer-Tropsch derived base oil has a kinematic
viscosity at 100.degree. C. of at most 5.0 mm.sup.2/s, preferably
at most 4.5 mm.sup.2/s, more preferably at most 4.2 mm.sup.2/s
(e.g. "GTL 4"). In another embodiment of the present invention, the
Fischer-Tropsch derived base oil has a kinematic viscosity at
100.degree. C. of at most 8.5 mm.sup.2/s, preferably at most 8
mm.sup.2/s (e.g. "GTL 8").
[0049] Further, the Fischer-Tropsch derived base oil typically has
a kinematic viscosity at 40.degree. C. (as measured by ASTM D445)
of from 10 to 100 mm.sup.2/s (cSt), preferably from 15 to 50
mm.sup.2/s.
[0050] Also, the Fischer-Tropsch derived base oil preferably has a
pour point (as measured according to ASTM D 5950) of -24.degree. C.
or below, more preferably below -30.degree. C., even more
preferably below -40.degree. C., and most preferably below
-45.degree. C.
[0051] The flash point (as measured by ASTM D92) of the
Fischer-Tropsch derived base oil is preferably greater than
120.degree. C., more preferably even greater than 140.degree.
C.
[0052] The Fischer-Tropsch derived base oil preferably has a
viscosity index (according to ASTM D 2270) in the range of from 100
to 200. Preferably, the Fischer-Tropsch derived base oil has a
viscosity index of at least 125, preferably 130. Also it is
preferred that the viscosity index is below 180, preferably below
150.
[0053] In the event the Fischer-Tropsch derived base oil contains a
blend of two or more Fischer-Tropsch derived base oils, the above
values apply to the blend of the two or more Fischer-Tropsch
derived base oils.
[0054] The lubricating oil composition described herein preferably
comprises 80 wt % or greater of Fischer-Tropsch derived base
oil.
[0055] Poly-alpha olefin base oils (PAOs) and their manufacture are
well known in the art. Suitable poly-alpha olefin base oils that
may be used include those 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.
[0056] Preferably, the base oil comprises mineral oils and/or
synthetic oils which contain more than 80 wt % of saturates,
preferably more than 90 wt %, as measured according to ASTM
D2007.
[0057] It is further preferred that the base oil contains less than
1.0 wt %, preferably less than 0.03 wt % of sulfur, calculated as
elemental sulfur and measured according to ASTM D2622, ASTM D4294,
ASTM D4927 or ASTM D3120.
[0058] Preferably, the viscosity index of the base oil is more than
80, more preferably more than 120, as measured according to ASTM
D2270.
[0059] Preferably, the base oil preferably has a kinematic
viscosity at 100.degree. C. of at least 2.5 mm.sup.2/s (according
to ASTM D445), preferably at least 3 mm.sup.2/s. In some
embodiments, the base oil has a kinematic viscosity at 100.degree.
C. of between 3.0 and 4.5 mm.sup.2/s.
[0060] The total amount of base oil incorporated in the lubricant
compositions is preferably in an amount in the range of from 60 to
99 wt %, more preferably in an amount in the range of from 65 to 90
wt % and most preferably in an amount in the range of from 75 to 88
wt %, with respect to the total weight of the lubricant
composition.
Performance Additives
[0061] Additionally, the lubricant compositions may further
comprise one or more performance additives such as anti-oxidants,
anti-wear additives, detergents, dispersants, friction modifiers,
viscosity index improvers, pour point depressants, corrosion
inhibitors, anti-foam agents, extreme pressure additives, metal
passivators and seal fix/seal compatibility agents.
[0062] Examples of suitable anti-oxidants include, but are not
limited to, aminic antioxidants, phenolic antioxidants, and
mixtures thereof. Examples of aminic antioxidants which may be
conveniently used include alkylated diphenylamines,
phenyl-.alpha.-naphthylamines, phenyl-.beta.-naphthylamines and
alkylated .alpha.-naphthylamines.
[0063] Preferred aminic antioxidants include dialkyldiphenylamines
such as p,p'-dioctyl-diphenylamine,
p,p'-di-.alpha.-methylbenzyl-diphenylamine and
N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such
as mono-t-butyldiphenylamine and mono-octyldiphenylamine,
bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and
di(2-ethyl-4-nonylphenyl)amine, alkylphenyl-1-naphthylamines such
as octylphenyl-1-naphthylamine and
n-t-dodecylphenyl-1-naphthylamine, 1-naphthylamine,
arylnaphthylamines such as phenyl-1-naphthylamine,
phenyl-2-naphthylamine, N-hexylphenyl-2-naphthylamine and
N-octylphenyl-2-naphthylamine, phenylenediamines such as
N,N'-diisopropyl-p-phenylenediamine and
N,N'-diphenyl-p-phenylenediamine, and phenothiazines such as
phenothiazine and 3,7-dioctylphenothiazine.
[0064] Preferred aminic antioxidants include those available under
the following trade designations: "Sonoflex OD-3" (ex. Seiko Kagaku
Co.), "Irganox L-57" (ex. Ciba Specialty Chemicals Co.) and
phenothiazine (ex. Hodogaya Kagaku Co.).
[0065] Examples of phenolic antioxidants which may be conveniently
used include C.sub.7-C.sub.9 branched alkyl esters of
3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid,
2-t-butylphenol, 2-t-butyl-4-methylphenol,
2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol,
2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone,
2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol,
2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol,
2,6-di-t-butyl-4-alkoxyphenols such as
2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,
3,5-di-t-butyl-4-hydroxybenzylmercaptooctylacetate,
alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such as
n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
n-butyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,6-d-t-butyl-.alpha.-dimethylamino-p-cresol,
2,2'-methylene-bis(4-alkyl-6-t-butylphenol) such as
2,2'-methylenebis(4-methyl-6-t-butylphenol, and
2,2-methylenebis(4-ethyl-6-t-butylphenol), bisphenols such as
4,4'-butylidenebis(3-methyl-6-t-butylphenol,
4,4'-methylenebis(2,6-di-t-butylphenol),
4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane,
2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-t-butylphenol),
hexamethyleneglycol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate],
triethyleneglycolbis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate],
2,2'-thio-[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionylo-
xy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane,
4,4'-thiobis(3-methyl-6-t-butylphenol) and
2,2'-thiobis(4,6-di-t-butylresorcinol), polyphenols such as
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
bis-[3,3'-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol
ester,
2-(3',5'-di-t-butyl-4-hydroxyphenyl)methyl-4-(2'',4''-di-t-butyl-3''-hydr-
oxyphenyl)methyl-6-t-butylphenol and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, and
p-t-butylphenol-formaldehyde condensates and
p-t-butylphenol-acetaldehyde condensates.
[0066] Examples of suitable phenolic antioxidants include those
which are commercially available under the following trade
designations: "Irganox L-135" (ex. Ciba Specialty Chemicals Co.),
"Yoshinox SS" (ex. Yoshitomi Seiyaku Co.), "Antage W-400" (ex.
Kawaguchi Kagaku Co.), "Antage W-500" (ex. Kawaguchi Kagaku Co.),
"Antage W-300" (ex. Kawaguchi Kagaku Co.), "Irganox L109" (ex. Ciba
Speciality Chemicals Co.), "Tominox 917" (ex. Yoshitomi Seiyaku
Co.), "Irganox L115" (ex. Ciba Speciality Chemicals Co.),
"Sumilizer GA80" (ex. Sumitomo Kagaku), "Antage RC" (ex. Kawaguchi
Kagaku Co.), "Irganox L101" (ex. Ciba Speciality Chemicals Co.),
"Yoshinox 930" (ex. Yoshitomi Seiyaku Co.).
[0067] In a preferred embodiment, antioxidants are present in an
amount in the range of from 0.1 to 5.0 wt %, more preferably in an
amount in the range of from 0.3 to 3.0 wt %, and most preferably in
an amount in the range of from 0.5 to 1.5 wt %, based on the total
weight of the lubricant composition.
[0068] Anti-wear additives that may be conveniently used include
zinc-containing compounds such as zinc dithiophosphate compounds
selected from zinc dialkyl-, diaryl- and/or
alkylaryl-dithiophosphates, molybdenum-containing compounds,
boron-containing compounds and ashless anti-wear additives such as
substituted or unsubstituted thiophosphoric acids, and salts
thereof.
[0069] Zinc dithiophosphate is a well known additive in the art and
may be conveniently represented by general formula II:
##STR00002##
wherein R.sup.2 to R.sup.5 may be the same or different and are
each a primary alkyl group containing from 1 to 20 carbon atoms
preferably from 3 to 12 carbon atoms, a secondary alkyl group
containing from 3 to 20 carbon atoms, preferably from 3 to 12
carbon atoms, an aryl group or an aryl group substituted with an
alkyl group, said alkyl substituent containing from 1 to 20 carbon
atoms preferably 3 to 18 carbon atoms.
[0070] Zinc dithiophosphate compounds in which R.sup.2 to R.sup.5
are all different from each other can be used alone or in admixture
with zinc dithiophosphate compounds in which R.sup.2 to R.sup.5 are
all the same.
[0071] Examples of suitable zinc dithiophosphates include those
which are commercially available under the following trade
designations: "Lz 1097", "Lz 1395", "Lz 677A", "Lz 1095", "Lz
1370", "Lz 1371", and "Lz 1373" (ex. Lubrizol Corporation); "OLOA
267", "OLOA 269R", "OLOA 260" and "OLOA 262" (ex. Chevron Oronite);
and "HITEC 7197" and "HITEC 7169" (ex. Afton Chemical).
[0072] Examples of molybdenum-containing compounds may conveniently
include molybdenum dithiocarbamates, trinuclear molybdenum
compounds, for example as described in WO 98/26030, sulphides of
molybdenum and molybdenum dithiophosphate.
[0073] Boron-containing compounds that may be conveniently used
include borate esters, borated fatty amines, borated epoxides,
alkali metal (or mixed alkali metal or alkaline earth metal)
borates and borated overbased metal salts.
[0074] The lubricant compositions may generally comprise in the
range of from 0.4 to 1.2 wt % of an anti-wear additive, based on
the total weight of the lubricant composition.
[0075] Typical detergents that may be used in the lubricating
compositions include one or more salicylate and/or phenate and/or
sulphonate detergents.
[0076] However, as metal organic and inorganic base salts which are
used as detergents can contribute to the sulfated ash content of a
lubricant composition, in a preferred embodiment, the amounts of
such additives are minimised. Furthermore, in order to maintain a
low sulphur level, salicylate detergents are preferred.
[0077] In order to maintain the total sulfated ash content of the
lubricant composition at a level of preferably not greater than 2.0
wt %, more preferably at a level of not greater than 1.0 wt % and
most preferably at a level of not greater than 0.8 wt %, based on
the total weight of the lubricant composition, said detergents are
preferably used in amounts in the range of 0.05 to 20.0 wt %, more
preferably from 1.0 to 10.0 wt % and most preferably in the range
of from 2.0 to 5.0 wt %, based on the total weight of the lubricant
composition.
[0078] Furthermore, the detergents may independently have a TBN
(total base number) value in the range of from 10 to 500 mgKOH/g,
more preferably in the range of from 30 to 350 mgKOH/g and most
preferably in the range of from 50 to 300 mgKOH/g, as measured by
ISO 3771.
[0079] The lubricant compositions may additionally contain an
ash-free dispersant which is preferably admixed in an amount in the
range of from 5 to 15 wt %, based on the total weight of the
lubricant composition.
[0080] 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.
[0081] Examples of viscosity index improvers which may be
conveniently used in the lubricant compositions 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 wt %, based on
the total weight of the lubricant composition.
[0082] Polymethacrylates may be conveniently employed in the
lubricant compositions as effective pour point depressants. For
corrosion inhibitors, it is possible to use alkenyl succinic acid
or ester moieties thereof, benzotriazole-based compounds and
thiodiazole-based compounds.
[0083] Compounds such as polysiloxanes, dimethyl polycyclohexane
and polyacrylates may be conveniently used in the lubricant
compositions as anti-foam agents.
[0084] Compounds which may be conveniently used in the lubricant
compositions as seal fix or seal compatibility agents include, for
example, commercially available aromatic esters.
[0085] The lubricant compositions may be conveniently prepared
using conventional formulation techniques by admixing one or more
base oils with one or more performance additives.
[0086] The present invention also relates to a method for advancing
the spark timing of a spark-ignition internal combustion engine,
the method comprising lubricating the spark-ignition internal
combustion engine with a lubricating composition comprising base
oil and anti-knock additive, wherein the anti-knock additive is an
aromatic amine. The advancement of spark timing provides benefits
in terms of reduced fuel flow requirement of the engine and reduced
brake specific fuel consumption of the engine.
[0087] The present invention further relates to a method for
advancing the spark timing of a spark-ignition internal combustion
engine, the method comprising lubricating the engine with a
lubricating composition, wherein the method further comprises a
step of adding an anti-knock additive to the lubricating
composition, wherein the anti-knock additive is an aromatic
amine.
[0088] In one embodiment of the present invention, the step of
adding an anti-knock additive to the lubricating composition is
achieved via transfer from the fuel composition. Hence, in such an
embodiment the step of adding an anti-knock additive to the
lubricating composition comprises the steps of (i) fuelling the
spark-ignition internal combustion engine with a fuel composition
comprising a base fuel and an anti-knock additive, wherein the
anti-knock additive is an aromatic amine, and (ii) transfer of
anti-knock additive during operation of the engine from the fuel
composition to the lubricating composition.
[0089] Transfer of anti-knock additive from the fuel composition to
the lubricating composition in the sump can occur, for example, via
one or more of the following possible mechanisms: entrainment in
blowby flow; evaporation from liner and piston; valve guide
leakage; leakage from turbocharger oil seals; and/or oil loss via
piston ring (see SAE paper SAE 2012-01-1617 by Arnault/Bonne,
"Engine Lube-Oil Consumption Takes and Benefits from Significant
Blow-by Oil Mist Reduction"). Transfer of anti-knock additive from
the fuel composition to the lubricating composition in the sump has
the advantage that the lubricating composition can be constantly
topped up with anti-knock additive. This is especially useful since
the anti-knock additive may have a tendency to degrade during use
and/or be combusted.
[0090] In another embodiment, the step of adding an anti-knock
additive to the lubricating composition is achieved via addition of
the anti-knock additive directly to the lubricating composition
(i.e. not via transfer from the fuel composition), for example by
adding the anti-knock additive during manufacture of the
lubricating composition, or by adding the anti-knock additive
directly to the lubricating composition in the sump.
Fuel Composition
[0091] The fuel compositions used in the present invention are
liquid fuel compositions, preferably gasoline fuel compositions
comprising a gasoline base fuel.
[0092] In one embodiment of the present invention, as mentioned
above, the anti-knock additive is included as an additive in the
fuel composition, and transferred from the fuel composition to the
lubricating composition during operation of the engine. In this
embodiment, the anti-knock additive is present in the fuel
composition so as to provide a certain level of anti-knock additive
in the lubricant.
[0093] In one embodiment of the present invention, the anti-knock
additive is present in the fuel composition in an amount so as to
provide a level of anti-knock additive in the lubricating
composition of preferably from 0.01 to 20 wt %, more preferably
from 0.1 to 10 wt %, even more preferably from 1 to 10 wt %, and
especially from 5 to 10 wt %, by weight of the lubricating
composition.
[0094] In another embodiment of the present invention, the
anti-knock additive is present in the fuel composition in an amount
so as to provide a level of anti-knock additive in the lubricating
composition of preferably from 3 to 20 wt %, more preferably from 5
to 20 wt %, even more preferably from 5 to 15 wt %, and especially
from 10 to 15 wt %, by weight of the lubricating composition.
[0095] The anti-knock additive is present in the fuel composition
preferably at a level of from 0.0005 to 5 vol %, more preferably at
a level of from 0.005 to 5 vol %, even more preferably at a level
of from 0.005 to 0.5 vol % and especially at a level of from 0.05
to 0.5 vol %.
[0096] The gasoline used as the gasoline base fuel 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 used herein may conveniently also be
referred to as `base gasoline`.
[0097] The gasoline base fuel may itself comprise a mixture of two
or more different gasoline fuel components, and/or be additivated
as described below.
[0098] Conventionally gasoline base fuels are present in a gasoline
or liquid fuel composition in a major amount, for example greater
than 50 wt % of the liquid fuel composition, and may be present in
an amount of up to 90 wt %, or 95 wt %, or 99 wt %, or 99.9 wt %,
or 99.99 wt %, or 99.999 wt %. Suitable the liquid fuel composition
contains or consists essentially of the gasoline base fuel, and
optionally one or more conventional gasoline fuel additives, such
as specified hereinafter.
[0099] 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.
[0100] The specific distillation curve, hydrocarbon composition,
research octane number (RON) and motor octane number (MON) of the
gasoline are not critical.
[0101] Conveniently, the research octane number (RON) of the
gasoline base fuel may be at least 80, for instance in the range of
from 80 to 130. Typically, the RON of the gasoline base fuel will
be at least 90, for instance in the range of from 90 to 120.
Typically, the RON of the gasoline base fuel will be at least 91,
for instance in the range of from 91 to 115 (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. Typically, the MON
of the gasoline will be at least 75, for instance in the range of
from 75 to 105, (EN 25163).
[0102] The liquid fuel composition used in the present invention
has a Research Octane Number (RON) of 95 or less, preferably of 93
or less, more preferably 92 or less, even more preferably 90 or
less. The liquid fuel composition used in the present invention has
a Motor Octane Number in the range of from 75 to 90.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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.
[0107] 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.
[0108] 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).
[0109] 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 wt % (EN 1601) (e.g. ethanol per se) based on the
gasoline. For example, the oxygen content of the gasoline may be up
to 25 wt %, preferably up to 10 wt %. 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 wt %, and a maximum
concentration selected from any one of 5, 4.5, 4.0, 3.5, 3.0, and
2.7 wt %.
[0110] 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.
[0111] 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.
[0112] 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 wt % (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.
[0113] 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.
[0114] 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. 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.
[0115] 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.
[0116] 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 wt %, 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.
[0117] As stated above, the gasoline composition may also contain
synthetic or mineral carrier oils and/or solvents.
[0118] 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 isomerised and also deparaffinised).
[0119] 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.
[0120] Examples of suitable polyolefins are olefin polymers, in
particular based on polybutene or polyisobutene (hydrogenated or
nonhydrogenated).
[0121] 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.
[0122] 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.
[0123] 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.
[0124] 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.
[0125] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-10 102 913.6.
[0126] Mixtures of mineral carrier oils, synthetic carrier oils,
and mineral and synthetic carrier oils may also be used.
[0127] 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).
[0128] 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.
[0129] 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 stabilisers, 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;
methylcyclo-pentadienylmanganese tricarbonyl; lubricity additives,
such as certain fatty acids, alkenylsuccinic esters,
bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil;
organic sunscreens or UV filter compounds; 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.
[0130] The gasoline compositions herein can also comprise a
detergent additive. Suitable detergent additives include those
disclosed in WO2009/50287, incorporated herein by reference.
[0131] In the above, amounts (concentrations, % vol, ppmw, wt %) of
components are of active matter, i.e. exclusive of volatile
solvents/diluent materials.
[0132] The invention is further described by reference to the
following non-limiting examples.
Examples
[0133] The lubricant composition used as a reference oil
(Comparative Example 1) in the following set of experiments was a
commercially available 5W-30 oil meeting ILSAC GF-5
specification.
[0134] Comparative Example 2 consisted of the same oil used in
Comparative Example 1 with the addition of a solubilising agent,
Priolube 1940, commercially available from Croda. Priolube 1940
does not give any octane boost itself.
[0135] Example 1 consisted of the same reference oil used in
Comparative Example 1 with the addition of anti-knock additive
1,2,3,4-tetrahydroquinoline (THQ) (commercially available from
Sigma Aldrich) dissolved in Priolube 1940. 742 g of THQ was
dissolved in 1.5 litres of Priolube 1940. This was added to the oil
of Comparative Example 1 so as to provide a concentration of
anti-knock additive in the sump of approximately 10 wt % (assuming
the sump is 8 litres).
[0136] Example 2 consisted of the same reference oil used in
Comparative Example 1 with the addition of anti-knock additive
N-methyl aniline, commercially available from Sigma Aldrich)
dissolved in Priolube 1940. 742 g of N-methyl aniline (750 ml) was
dissolved in 1.5 litres of Priolube 1940 (50 wt %). This was added
to the reference oil of Comparative Example 1 so as to provide a
concentration of anti-knock additive in the sump of approximately
10 wt % (assuming the sump volume is 8 litres).
[0137] The fuel used in the following experiments was an AKI 87 E10
fuel having the properties detailed in Table 1 below.
TABLE-US-00001 TABLE 1 Properties of Fuel Test Property Method
Units Result RVP ASTM D- kPa 48.13 5191 Aromatic ASTM D- % 19.2
1319 Olefins ASTM D- % 11 1319 Saturate ASTM D- % 69.8 1319 Gross
MJ/kg 44.757 heating value RON ASTM D- 91.4 2699 MON ASTM D- 82.9
2700 AKI 87.1 Unwashed ASTM D- 16 Gum 381 Washed ASTM D- <0.5
mg/ Gum 381 100 mL Specific ASTM D- g/ml 0.7428 Gravity 4052
@15.degree. C. Density g/ml 0.7426 at 15.degree. C. Carbon ASTM D-
wt % 82.46 5291 Hydrogen ASTM D- wt % 13.98 5291 Sulphur ASTM D-
mg/kg 14.9 5433 EtOH ASTM D- vol % 9.688 5599 Water % 0.13414 IBP
ASTM D- .degree. C. 39.4 86 Evap_5 .degree. C. 54.4 Evap_10
.degree. C. 57.9 Evap_15 .degree. C. 60.2 Evap_20 .degree. C. 62.5
Evap_30 .degree. C. 66.3 Evap_40 .degree. C. 74.4 Evap_50 .degree.
C. 101.7 Evap_60 .degree. C. 114.2 Evap_70 .degree. C. 125.9
Evap_80 .degree. C. 142.2 Evap_90 .degree. C. 167.2 Evap_95
.degree. C. 184.4 FBP .degree. C. 207.2 Recovered mL 97.8 Residue
mL 1.3 Loss mL 0.9
[0138] The engine used in the following experiments was a Ford
EcoBoost 3.5 L, V6 turbocharged direct injection spark ignition
engine installed with a development engine control unit (ECU) with
production engine calibration.
[0139] Table 2 below shows an overview of the test procedure that
was used in the experiments.
TABLE-US-00002 TABLE 2 Test Procedure Duration Culmination Part
Stage Activity (min) (min) 1. Preparation If it is not 20 20 still
warm from the over-night de-greening procedure, the vehicle is
warmed up 2. Fuel fill Fuel tank is 10 30 topped up with fuel 3.
Lube fill Sump is 40 70 emptied with three flushes and refilled
with fresh baseline lubricant (Comparative Example 1) 4.
Stabilisation, Test 20 90 first half Protocol (Stage 1a) (Table 3)
is followed 5. Pause in Engine is 10 100 stabilisation turned off
6. Stabilisation, Test 20 120 second half Protocol (Stage 1b)
(Table 3) is followed 7. Fuel exchange Engine is 40 160 turned off,
leaving oil to cool for 15 min, two litres of used reference oil
(Comparative Example 1) are removed from the oil drain plug and
replaced with a blend of one and a half litres of test lubricant
(Comparative Examples 1 and 2 and Examples 1-2) and half a litre of
recovered used reference oil (Comparative Example 1) 8. Test, first
Engine is 30 190 half (Stage turned off 2a) 9. Pause in test Engine
is 20 210 turned off 10. Test, second Test 30 240 half (Stage
Protocol 2b) (Table 3) is followed whilst taking measurements.
TABLE-US-00003 TABLE 3 Test Protocol Engine Speed Test Step (rpm)
BMEP (bar) Time (min) 1 1500 4 1 2 1500 12 3 3 2000 16 3 4 3000 17
3 5 2000 2 1 6 Transient WOT 5 Portion 7 1500 12 3 8 2000 16 3 9
3000 17 3 10 2000 2 1 11 Transient WOT 5 Portion 12 1250 (cool 2 4
down) Total Stage Duration 35
[0140] The Transient Portion of the Test Protocol consists of 10
accelerations in 300 seconds starting at 2000 and ending at 5000
rpm with a torque of 475 Nm.
[0141] Various parameters were logged every deci-second including
Spark timing (CAD), Fuel flow rate (kg/h) and Brake Specific Fuel
Consumption (BSFC) (g/kWh). The results are detailed below.
Results
[0142] An advance of 0.7 CAD was established at 1500 rpm for THQ
(Example 1) and NMA (Example 2) and an advance of 0.3 CAD was
established at 3000 rpm for NMA (Example 2).
TABLE-US-00004 TABLE 4 Effect of spark advance on fuel flow rate
and brake specific fuel consumption (BSFC) % Benefit over 1500 rpm
3000 rpm Comparative Fuel Fuel Example 1 flow BSFC flow BSFC
Example 1 0.87 0.94 1.03 1.04 Example 2 1.49 1.49 1.36 1.36
[0143] As can be seen from Table 4, the benefits of spark timing
advance provided by methods of the present invention leads to
benefits in fuel flow requirement and brake specific fuel
consumption over the reference oil.
[0144] No benefit in spark timing, fuel flow requirement or brake
specific fuel consumption was seen for Comparative Example 1
(reference oil) or for Comparative Example 2 (reference oil with
the addition of solubilising agent Priolube 1940).
* * * * *