U.S. patent application number 15/510489 was filed with the patent office on 2017-09-14 for additive and fuel compositions.
The applicant listed for this patent is BP OIL INTERNATIONAL LIMITED. Invention is credited to Robert Edward ALLAN, David Michael WILLIAMSON.
Application Number | 20170260468 15/510489 |
Document ID | / |
Family ID | 51869466 |
Filed Date | 2017-09-14 |
United States Patent
Application |
20170260468 |
Kind Code |
A1 |
ALLAN; Robert Edward ; et
al. |
September 14, 2017 |
ADDITIVE AND FUEL COMPOSITIONS
Abstract
An additive composition, on use in a fuel in a spark-ignition
internal combustion engine, controls the formation of sludge and
piston varnish. When used in a direct injection spark-ignition
internal combustion engine, particulate emissions and deposit
formation on intake valves may also be controlled. When used in a
port fuel injection spark-ignition internal combustion engine, the
port fuel injection valve deposits may be reduced. The additive
composition comprises a polyalkylene amine and a
hydrocarbyl-substituted hydroxyaromatic compound. The additive
compositions may be present in a fuel composition.
Inventors: |
ALLAN; Robert Edward;
(Middlesex, GB) ; WILLIAMSON; David Michael;
(Middlesex, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BP OIL INTERNATIONAL LIMITED |
Middlesex |
|
GB |
|
|
Family ID: |
51869466 |
Appl. No.: |
15/510489 |
Filed: |
September 10, 2015 |
PCT Filed: |
September 10, 2015 |
PCT NO: |
PCT/EP2015/070689 |
371 Date: |
March 10, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 10/06 20130101;
C10L 2270/023 20130101; C10L 10/04 20130101; C10L 1/2383 20130101;
C10L 10/02 20130101; C10L 1/146 20130101; C10L 1/1985 20130101;
C10L 1/238 20130101 |
International
Class: |
C10L 1/14 20060101
C10L001/14; C10L 10/02 20060101 C10L010/02; C10L 10/06 20060101
C10L010/06; C10L 10/04 20060101 C10L010/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 11, 2014 |
GB |
1416088.1 |
Claims
1-12. (canceled)
13. An additive composition for use in a fuel for a spark-ignition
internal combustion engine or a compression-ignition gasoline
internal combustion engine, said additive composition comprising:
about 5% to about 55% by weight of a polyalkylene amine, said
polyalkylene amine comprising a polyalkylene group that exhibits a
number average molecular weight of from about 700 to about 1500;
and about 3% to about 25% by weight of a hydrocarbyl-substituted
hydroxyaromatic compound, said hydrocarbyl-substituted aromatic
compound comprising a hydrocarbyl group that exhibits a number
average molecular weight of from about 700 to about 1500 and has up
to about 60 mol % vinylidene terminal groups.
14. The additive composition of claim 13, where said additive
composition comprises: about 5% to about 25% by weight of a
polyether carrier fluid.
15. The additive composition of claim 13, wherein the
hydrocarbyl-substituted aromatic compound is a Mannich Base
additive.
16. The additive composition of claim 13, wherein the polyalkylene
amine is a polyisobutylene amine.
17. The additive composition of additive composition of claim 13,
wherein the hydrocarbyl substituent of the aromatic compound is or
comprises polyisobutylene.
18. The additive composition of claim 13, wherein the weight ratio
of actives of the polyalkylene amine : the hydrocarbyl-substituted
aromatic compound is in the range of from about 5:1 to about
1:5.
19. The additive composition of claim 13, wherein the a polyether
carrier fluid is used at weight ratio of actives of the polyether
carrier fluid : the combination of the polyalkylene amine and the
hydrocarbyl-substituted aromatic compound is greater than about
1:2.
20. The additive composition of claim 13, wherein the polyalkylene
amine comprises a polyalkylene group having at least about 60 mol %
vinylidene terminal groups.
21. A fuel composition for use in a spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine, said fuel composition comprising: about 50 ppm
to about 300 ppm by weight of a polyalkylene amine, said
polyalkylene amine comprising a polyalkylene group that exhibits a
number average molecular weight of from about 700 to about 1500;
and about 20 ppm to about 200 ppm by weight of a
hydrocarbyl-substituted hydroxyaromatic compound, said
hydrocarbyl-substituted aromatic compound comprising a hydrocarbyl
group that exhibits a number average molecular weight of from about
700 to about 1500 and has up to about 60 mol % vinylidene terminal
groups.
22. The fuel composition of claim 21, wherein said fuel composition
comprises: about 20 ppm to about 300 ppm polyether carrier
fluid.
23. The fuel composition of claim 21, wherein the
hydrocarbyl-substituted aromatic compound is a Mannich Base
additive.
24. The fuel composition of claim 21, wherein the polyalkylene
amine is a polyisobutylene amine.
25. The fuel composition of claim 21, wherein the hydrocarbyl
substituent of the aromatic compound is or comprises
polyisobutylene.
26. The fuel composition of claim 21, wherein the weight ratio of
actives of the polyalkylene amine:the hydrocarbyl-substituted
aromatic compound is in the range of from about 5:1 to about
1:5.
27. The fuel composition of claim 21, wherein the a polyether
carrier fluid is used at weight ratio of actives of the polyether
carrier fluid:the combination of the polyalkylene amine and the
hydrocarbyl-substituted aromatic compound is greater than about
1:2.
28. The fuel composition of claim 21, wherein the polyalkylene
amine comprises a polyalkylene group having at least about 60 mol %
vinylidene terminal groups.
29. An additive composition, which additive composition, on use in
a fuel in a spark-ignition internal combustion engine, controls the
formation of sludge and piston varnish; and which additive
composition, when used in a direct injection spark-ignition
internal combustion engine, controls particulate emissions and
deposit formation on intake valves; and which additive composition,
when used in a port fuel injection spark-ignition internal
combustion engine, reduces the port fuel injection valve
deposits.
30. A fuel composition containing the additive composition of claim
29.
Description
[0001] This invention relates to a multi-purpose additive
composition for a spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine, as well
as fuels for a spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine containing
said additive. The invention also relates to the beneficial effects
exhibited by the additive composition when used in the engine.
[0002] In general, there are two types of spark-ignition, internal
combustion engines which are classified according to the type of
system for delivering fuel to the engine combustion chambers:
[0003] Port Fuel Injection (PFI) engines--engines in which a
mixture of fuel and air is injected into intake ports and then
passes into combustion chambers of the engine through one or more
intake valves (sometimes also called inlet valves or inlet port
valves). [0004] Direct Injection (DI) engines--engines in which
fuel is injected directly into combustion chambers of the engine
through injectors (sometimes also called direct injectors or direct
injector nozzles) and air is introduced into the combustion
chambers through one or more air intake valves (sometimes also
called air inlet valves or air inlet port valves).
[0005] Deposits in the fuel delivery system of a port fuel
injection spark-ignition internal combustion engine may adversely
affect the performance of the engine, for example in respect of
driveability including for example power output and
acceleration.
[0006] In direct injection spark-ignition internal combustion
engines, intake valve deposits (IVD) may accumulate on the intake
valves used to control intake of air into the combustion chambers.
Although in some direct injection engines, in certain operating
conditions, fuel may be passed over the air intake valves from time
to time, in general, these inlet or intake valves of direct
injection engines are not usually subject to (and hence cannot
benefit from) a flow of fuel through the intake valves. Instead,
the fuel is injected into the combustion chambers separately from
the air, through direct injectors (sometimes also called direct
injector nozzles). Deposits on the air intake valves of a direct
injection spark-ignition internal combustion engine may adversely
affect the performance of the engine.
[0007] Particles that are produced during fuel combustion can also
impact the performance of an engine. For instance, they can lead to
wear on components of the engine, clogging of engine components, as
well as octane requirement increase, greater propensity for
pre-ignition in the engine and increases in turbo lag and response
times in the engine. It is also well known that vehicle emissions
including particles may have an effect on air quality. The number
of particles emitted from gasoline direct injection engines is now
being mandated by legislation. An example of this is EU Commission
Regulation No 582/2011, known as `The Euro VI` emissions
regulation, which came into force on 31 Dec. 2013.
[0008] A further issue that may be encountered during operation of
a spark-ignition internal combustion engine is agglomeration of the
lubricant oil, creating a highly viscous tar-like material from the
degraded oil known as sludge. Piston varnish may also build up
during engine operation, typically more in areas of low metal
surface clearance (piston rubbing surface areas). Sludge and piston
varnish can reduce the performance of an engine. Typically,
formation of sludge and piston varnish has been controlled using
lubricating oils.
[0009] Additives compositions and fuels containing additive
compositions may mitigate certain problems associated with running
an engine. However, certain fuels may only exhibit beneficial
properties in one of a port fuel injection engine or a direct
injection engine. Moreover, while certain fuels may benefit certain
engine functions, they may fail to alleviate issues encountered
with other engine functions.
[0010] Accordingly, there is a need for an additive composition and
a fuel composition which mitigates a range of problems that are
encountered in direct injection spark-ignition internal combustion
engines and port fuel injection spark-ignition internal combustion
engines.
[0011] According to its abstract, U.S.2003/0029077 relates to a
fuel composition comprising a hydrocarbon fuel, a combination of
nitrogen-containing detergents that includes a
hydrocarbyl-substituted polyamine and a Mannich reaction product,
and optionally a fluidizer. Methods of operating and of controlling
deposits in an internal combustion engine involve fuelling the
engine with the fuel composition which is said to result in control
of deposits in the fuel induction system.
[0012] According to its paragraph [0002], U.S.2006/0277820 relates
to a deposit control additive composition for a fuel comprising
polyisobutylene amine (PIBA) having an average molecular weight of
about 700 to about 1000 and a Mannich Base as synergistic
components of the deposit control additive formulation.
[0013] Paragraph [0015] of U.S. 2006/0277820 states: [0014]
"Mannich bases have been used in isolation or in combination with
diamine to reduce deposits on carbure[t]tor surfaces. As disclosed
in the present application, a surprising result has been achieved
by using a Mannich base and Polyisobutylene amine as synergistic
components of a deposit control additive formulation to drastically
reduce deposits on carburet[t] or and keep port fuel injectors and
intake valves clean in gasoline fuel[l] ed spark ignition internal
combustion engines."
[0015] Paragraph [0069] of U.S.2006/0277820 relates to an Inlet
Valve Deposit Test using Mercedes Benz M111 Engine as per CEC
F-20-A-98 and paragraph [0070] relates to Port Fuel Injector
Fouling Bench Test.
[0016] There remains a need for additive compositions and fuels
which reduce or at least mitigate a number of problems typically
associated with running an engine, for example as identified
above.
[0017] According to a first aspect of the present invention there
is provided an additive composition for use in a fuel for a
spark-ignition internal combustion engine or a compression-ignition
gasoline internal combustion engine, said additive composition
comprising:
[0018] about 5% to about 55% by weight of a polyalkylene amine,
said polyalkylene amine comprising a polyalkylene group that
exhibits a number average molecular weight of from about 700 to
about 1500; and
[0019] about 3% to about 25% by weight of a hydrocarbyl-substituted
hydroxyaromatic compound, said hydrocarbyl-substituted aromatic
compound comprising a hydrocarbyl group that exhibits a number
average molecular weight of from about 700 to about 1500 and has up
to about 60 mol % vinylidene terminal groups.
[0020] According to a further aspect of the present invention there
is provided a fuel composition for use in a spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine, said fuel composition comprising:
[0021] about 50 ppm to about 300 ppm by weight of a polyalkylene
amine, said polyalkylene amine comprising a polyalkylene group that
exhibits a number average molecular weight of from about 700 to
about 1500; and
[0022] about 20 ppm to about 200 ppm by weight of a
hydrocarbyl-substituted hydroxyaromatic compound, said
hydrocarbyl-substituted aromatic compound comprising a hydrocarbyl
group that exhibits a number average molecular weight of from about
700 to about 1500 and has up to about 60 mol % vinylidene terminal
groups.
[0023] According to another aspect of the present invention there
is provided an additive composition, which additive composition, on
use in a fuel in a spark-ignition internal combustion engine,
controls the formation of sludge and piston varnish; and which
additive composition, when used in a direct injection
spark-ignition internal combustion engine, controls particulate
emissions and deposit formation on intake valves; and which
additive composition, when used in a port fuel injection
spark-ignition internal combustion engine, reduces the port fuel
injection valve deposits.
[0024] According to another aspect of the present invention a fuel
composition containing an additive composition of the present
invention is provided.
[0025] In embodiments, the hydrocarbyl-substituted aromatic
compound is a Mannich base additive. In embodiments, the
polyalkylene amine is a polyisobutylene amine.
[0026] Aspects of the present invention address the technical
problems identified and others, by the use in combination of a
hydrocarbyl-substituted aromatic compound and a polyalkylene
amine.
[0027] In particular, it has been found that when used in a
spark-ignition internal combustion engine, the additive composition
may control sludge formation and piston varnish formation. When
used in a direct injection spark-ignition internal combustion
engine, the additive composition may also control particulate
emission and deposit formation on intake valves. When used in a
port fuel injection spark-ignition internal combustion engine, the
additive composition may also reduce the port fuel injection valve
deposits.
Polyalkylene Amine.
[0028] The polyalkylene amine used in the present invention may
comprise a polyalkylene group having at least 60 mol % vinylidene
terminal groups, such as at least 70 mol % vinylidene terminal
groups or at least 80 mol % vinylidene terminal groups.
[0029] The polyalkylene amine may be a poly C.sub.1-10-alkylene
amine. For instance, the polyalkylene amine may be polyethylene
amine, a polypropylene amine, a polybutylene amine, a polypentylene
amine or a polyhexylene amine. In examples, the polyalkylene amine
is a polybutylene amine, in particular a polyisobutylene amine.
[0030] Polyisobutylene amines are also sometimes called
polyisobutylamine or PIBA. Examples of suitable polyisobutylene
amines include mono-amines, di-amines and polyamines of
polyisobutylene including for example, polyisobutylene that is a
homopolymer of isobutylene and polyisobutylene that is a polymer of
isobutylene with minor amounts (for example up to 20% by weight),
of one or more other monomers including for example n-butene,
propene and mixtures thereof.
[0031] Examples of suitable polyisobutylene amines include
polyisobutylene amines disclosed in, and/or obtained or obtainable
by methods described in, U.S. Pat. No. 4,832,702, U.S. Pat. No.
6,140,541, U.S. Pat. No. 6,909,018 and/or U.S. Pat. No.
7,753,970.
[0032] Examples of suitable polyisobutylene amines include
polyisobutylene amines disclosed in, and/or obtained or obtainable
by methods described in, U.S. Pat. No. 4,832,702. Thus, suitable
polyisobutylene amines include compounds represented by the
structural formula I:
##STR00001##
in which R.sub.1 is a polybutyl- or polyisobutyl group derivable or
derived from isobutene and up to 20% by weight of n-butene and
[0033] R.sub.2 and R.sub.3 are identical or different and are each
independently: [0034] hydrogen; [0035] an aliphatic or aromatic
hydrocarbyl group; [0036] a primary or secondary, aromatic or
aliphatic aminoalkylene group or polyaminoalkylene group; [0037] a
polyoxyalkylene group; [0038] a heteroaryl or heterocyclyl group;
or [0039] together with the nitrogen atom to which they are bonded
form a ring in which further hetero atoms may be present.
[0040] In at least some examples, R.sub.2 and R.sub.3 are identical
or different and are each independently: [0041] hydrogen; [0042]
alkyl; [0043] aryl; [0044] hydroxyalkyl; or [0045] an aminoalkylene
group represented by the general formula (II):
[0045] ##STR00002## [0046] wherein R.sub.4 is alkylene and R.sub.5
and R.sub.6 are identical or different and are each independently:
hydrogen; alkyl; aryl; hydroxyalkyl; polybutyl; or polyisobutyl; or
[0047] a polyaminoalkylene group represented by the general formula
(III):
[0047] [--R.sub.4--NR.sub.5].sub.m R.sub.6 (III) [0048] wherein the
R.sub.4 groups are the same or different and the R.sub.5 groups are
the same or different and R.sub.4, R.sub.5 and R.sub.6 have the
above meaning and m is an integer from 2 to 8; or [0049] a
polyoxyalkylene group represented by the general formula (IV):
[0049] [--R.sub.4--O--].sub.n X (IV) [0050] wherein the R.sub.4
groups are the same or different and have the above meaning, X is
alkyl or H and n is an integer from 1 to 30.
[0051] In at least some examples R.sub.2 and R.sub.3 together with
the nitrogen atom to which they are bonded form a morpholinyl,
pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrolinyl,
pyrrol-idinyl, pyrazinyl or pyridazinyl group.
[0052] In at least some examples R.sub.1 is a polybutyl or
polyisobutyl group containing 20 to 400 carbon atoms which is
derived or derivable from isobutene and up to 20% by weight
n-butene.
[0053] In at least some examples R.sub.1 is a polybutyl or
polyisobutyl group containing 32 to 200 carbon atoms which is
derived or derivable from isobutene and up to 20% by weight
n-butene and R.sub.2 and R.sub.3 identical or different and are
each independently: hydrogen, methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, phenyl,
--CH.sub.2--CH.sub.2--NH.sub.2,
--CH.sub.2--CH.sub.2--CH.sub.2--N(CH.sub.3).sub.2, or
--[--CH.sub.2--CH.sub.2--NH].sub.p --CH.sub.2--CH.sub.2--NH.sub.2
where p is an integer from 1 to 7, for example 1 to 3,
--CH.sub.2--CH.sub.2--OH,
--[--CH.sub.2--CH.sub.2--O].sub.q--CH.sub.2--OH where q is an
integer from 1 to 30, or together with the nitrogen atom to which
they are bonded, form a morpholinyl group.
[0054] Examples of suitable polyisobutylene amines additives also
include polyisobutylene amines disclosed in, and/or obtained or
obtainable by methods described in, described in U.S. Pat. No.
6,140,541 and U.S. Pat. No. 6,909,018. Thus, examples of suitable
polyisobutylene amines include compounds represented by the formula
(V):
##STR00003##
[0055] wherein R.sub.7, R.sub.8, R.sub.9 and R.sub.10 independently
of one another, are each hydrogen or an unsubstituted or
substituted, saturated or mono- or polyunsaturated aliphatic group
exhibiting a number average molecular weight of up to 40000, at
least one of the groups R.sub.7 to R.sub.10 exhibiting a number
average molecular weight of from 150 to 40000, and R.sub.11 and
R.sub.12 independently of each other are each H; an alkyl group,
for example a C.sub.1 to C.sub.18 alkyl group; a cycloalkyl group;
a hydroxyalkyl group; an aminoalkyl group; an alkenyl group; an
alkynyl group, an aryl group; an arylalkyl group; an alkylaryl
group; a heteroaryl group; an alkylene-imine group represented by
the formula (VI):
##STR00004##
wherein: [0056] Alk is a straight-chain or branched alkylene [0057]
m is an integer from 0 to 10; and [0058] R.sub.13 and R.sub.14,
independently of one another, are each H; an alkyl group, for
example a C.sub.1 to C.sub.18 alkyl group; a cycloalkyl group; a
hydroxyalkyl group; an aminoalkyl group; an alkenyl group; an
alkynyl group, an aryl group; an arylalkyl group; an alkylaryl
group; a heteroaryl group or, together with the nitrogen atom to
which they are bonded, form a heterocyclic structure, or
[0059] R.sub.11 and R.sub.12, together with the nitrogen atom to
which they are bonded, form a heterocyclic structure.
[0060] In at least some examples, each of R.sub.11, R.sub.12,
R.sub.13 and R.sub.14 are independently substituted by further
alkyl groups carrying hydroxy or amino groups.
[0061] Examples of suitable polyisobutylene amines additives also
include polyisobutylene amines disclosed in, and/or obtained or
obtainable by methods described in, U.S. Pat. No. 7,753,970. Thus,
examples of suitable polyisobutylene amines include polyisobutylene
amines that are derived or derivable from polyisobutenes derived or
derivable from isobutene or an isobutenic monomer mixture, for
example a mixture of isobutene and up to 20% by weight of n-butene.
Suitable polyisobutylene amines include polyisobutene amines
derived or derivable from polyisobutylene that is derived or
derivable by the polymerisation of identical or different
straight-chain or branched C.sub.4 olefin monomers, which in at
least some examples, are suitably randomised in the polymerisation
product. Suitable polyisobutylene amines include polyisobutylene
amines that are derived or derivable from highly reactive
polyisobutenes. Highly reactive polyisobutenes contain a high
content of terminal double bonds (also sometimes referred to
alpha-olefinic double bonds and/or vinylidene double bonds), for
example at least 20%, or at least 50%, or at least 70% of the total
olefinic double bonds in the polyisobutene. These are sometimes
represented by the general structure:
##STR00005##
[0062] Highly reactive polyisobutenes may be made by methods
described for example in U.S. Pat. No. 4,152,499.
[0063] In at least some examples the polyisobutylene amine contains
a polyisobutenic group that exhibits a number average molecular
weight of from about 200 to about 10000, for example from about 500
to about 5000 or from about 700 to about 1500 or from about 800 to
about 1200 or from about 850 to about 1100, for example about
1000.
[0064] In at least some examples, the polyisobutylene amine is
derived from or derivable from a polyisobutene that exhibits at
least one of the following properties: [0065] (i) being derivable
or derived from isobutene and up to 20% by weight of n-butene;
[0066] (ii) being derivable or derived from isobutenic mixture
containing at least 70 mol. % vinylidene double bonds based on the
total olefinic bonds in the polyisobutene; [0067] (iii) containing
at least 85% by weight isobutylene units; [0068] (iv) a
polydispersity in the range of from 1.05 to 7
[0069] Methods of making suitable polyisobutylene amines are
described for example in U.S. Pat. No. 4,832,702, U.S. Pat. No.
6,140,541, U.S. Pat. No. 6,909,018 and/or U.S. Pat. No.
7,753,970.
[0070] In at least some examples, more than one polyalkylene amine
is present/used. Where more than one polyalkylene amine is
present/used, each polyalkylene amine may be a polyisobutylene
amine.
[0071] The polyalkylene amine is used in the fuel composition at a
concentration of actives in the range of from about 50 ppm to about
300 ppm, such as from about 70 ppm to about 250 ppm. As will be
clear to the skilled person, the concentration of actives expressed
herein in terms of ppm is ppm by weight.
[0072] Typically, the polyalkylene amine will be used in the fuel
composition at a concentration of actives of from about 50 ppm to
about 160 ppm. In some examples, however, higher treat rates may be
used. In such instances, the polyalkylene amine may be present/used
in the fuel composition at a concentration of from about 160 ppm to
about 300 ppm.
[0073] The polyalkylene amine is used in the additive composition
at a concentration of actives in the range of from about 5% to
about 55%, such as from about 10% to about 50%.
[0074] Concentration of actives means the concentration of the
active polyalkylene amine disregarding for example, any solvent and
the like.
[0075] Where more than one polyalkylene amine is used, the total
concentration of the polyalkylene amines is as described
herein.
Hydrocarbyl-Substituted Aromatic Compound.
[0076] The hydrocarbyl-substituted aromatic compound used in the
present invention comprises a hydrocarbyl group having up to about
60 mol % vinylidene terminal groups, such as up to about 55 mol %
vinylidene terminal groups or up to about 50 mol % vinylidene
terminal groups. The hydrocarbyl group is preferably a polyalkylene
group. Accordingly, it will be appreciated that the additive
composition and fuel composition of the present invention may
contain a polyalkylene amine having higher reactivity polyalkylene
groups in combination with a hydrocarbyl-substituted aromatic
compound having lower reactivity polyalkylene groups.
[0077] The hydrocarbyl-substituted aromatic compound may be a
hydrocarbyl-substituted hydroxyaromatic compound, such as a
hydrocarbyl-substituted phenol compound. The hydrocarbyl
substituent may attach at the ortho-, meta- or para- position of
the phenol ring.
[0078] The hydrocarbyl substituent of the hydrocarbyl-substituted
aromatic compound may exhibit a number average molecular weight of
from about 700 to about 1500, such as from about 900 to about
1300.
[0079] In embodiments, a Mannich Base additive may be used as the
hydrocarbyl-substituted aromatic compound.
[0080] Examples of Mannich Base additives include those obtained or
obtainable by the reaction of a hydrocarbyl-substituted
hydroxyaromatic compound, an amine and an aldehyde under Mannich
condensation reaction conditions. Suitable reaction conditions
include at least one (for example, all) of the following
conditions: [0081] at a temperature in the range of from 40.degree.
C. to 200.degree. C.; in the absence or presence of solvent; [0082]
for a reaction time in the range of from 2 to 4 hours; and [0083]
with azeotropic distillative removal of water by-product.
[0084] Examples of aldehydes suitable for the preparation of
Mannich Base additives include: [0085] aliphatic aldehydes,
including for example, formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caprioaldehyde, heptaldehyde and
stearaldehyde; [0086] aromatic aldehydes including for example,
benzaldehyde and salicylaldehyde; and [0087] heterocyclic aldehydes
including for example, furfural aldehyde and thiophene
aldehyde.
[0088] Also useful in at least some examples are formaldehyde
precursors including for example paraformaldehyde and aqueous
formaldehyde solutions including for example formalin.
[0089] Examples of representative hydrocarbyl substituents of the
hydrocarbyl-substituted hydroxyaromatic compound include for
example, polyolefin polymers for example polypropylene,
polybutenes, polyisobutylene, ethylene alpha-olefin copolymers and
the like. Other examples include copolymers of butylene and/or
isobutylene and/or propylene and one or more mono-olefinic
comonomers copolymerisable therewith (for example ethylene,
1-pentene, 1-hexene, 1-octene, 1-decene and the like) where the
comonomer molecule contains at least 50% by weight of butylene
and/or isobutylene and/or propylene units. In some examples the
copolymers are aliphatic and in some examples contain non-aliphatic
groups (for example styrene, o-methylstyrene, p-methylstyrene,
divinyl benzene and the like), in any case the resulting polymers
are substantially aliphatic hydrocarbon polymers.
[0090] Examples of suitable Mannich Base additives include Mannich
Base additives in which the hydrocarbyl substituent of the aromatic
group is or comprises polyisobutylene. Such compounds are sometimes
called PIB-Mannich Base additives.
[0091] In at least some examples hydrocarbyl substituents of the
hydrocarbyl-substituted hydroxyaromatic compound include polymers
obtained or obtainable from pure or substantially pure 1-butene;
polymers obtained or obtainable from pure or substantially pure
isobutene; and polymers obtained or obtainable from mixtures of
1-butene, 2-butene and isobutene. In at least some examples the
hydrocarbyl-substituted hydroxyaromatic reactant is obtained or
obtainable from high reactive polyisobutene. High reactive
polyisobutenes contain a high content of terminal double bonds
(also sometimes referred to alpha-olefinic double bonds and/or
vinylidene double bonds), for example at least 20%, or at least
50%, or at least 70% of the total olefinic double bonds in the
polyisobutene. Examples of high reactivity polybutylenes containing
relatively high proportions of polymer molecules comprising a
terminal vinylidene group include those that are obtained or
obtainable by methods described in U.S. Pat. No. 4,152,499 and
DE2904314.
[0092] In at least some examples the hydrocarbyl substituents
contain some residual unsaturation but in general they are
substantially saturated.
[0093] In at least some examples the hydrocarbyl substituent is a
polymer exhibiting a polydispersity of from 1 to 4, for example
from 1 to 2, for example as determined by gel permeation
chromatography (sometimes also referred to as GPC).
[0094] In some examples, the hydrocarbyl substituent of the
hydroxyaromatic compound used to prepare the Mannich Base additive,
which in some instances is or comprises polyisobutylene, may
exhibit a number average molecular weight of from about 700 to
about 1500, such as from about 900 to about 1300.
[0095] Examples of suitable Mannich Base additives include those
disclosed in, and/or obtained or obtainable by methods described
in, U.S. Pat. No. 5,634,951, U.S. Pat. No. 5,697,988, U.S. Pat. No.
6,800,103, U.S. Pat. No. 7,597,726 and/or U.S.20090071065.
[0096] Examples of suitable Mannich Base additives include those
disclosed in, and/or obtained or obtainable by methods described
in, U.S. Pat. No. 5,634,951. Thus, examples of suitable Mannich
Base additives include those obtainable or obtained by the reaction
of (i) one mole part of at least one hydroxyaromatic compound
comprising on the ring an aliphatic hydrocarbyl substituent derived
from a polyolefin exhibiting a number average molecular weight in
the range of 500 to 3000, (ii) from 0.8 to 1.3 mole part(s) of at
least one aldehyde, and (iii) from 0.8 to 1.5 mole part(s) of at
least one aliphatic polyamine comprising in the molecule one
primary or secondary amino group capable of undergoing a Mannich
condensation reaction with (i) and (ii), the other amino group or
groups (if any) in the molecule being substantially inert towards
participation in such Mannich condensation reaction, with the
proviso that the mole ratio of aldehyde to amine is 1.2 or
less.
[0097] Examples of suitable hydroxyaromatic compounds (i) include
high molecular weight alkyl-substituted hydroxyaromatic compounds
including polypropylphenol (including those formed by alkylating
phenol with polypropylene), polybutylphenols (including those
formed by alkylating phenol with polybutenes and/or
polyisobutylene), and polybutyl-co-polypropylphenols (including
those formed by alkylating phenol with a copolymer of butylene
and/or isobutylene and propylene). Other hydroxyaromatic compounds
include for example, long chain alkylphenols for example those made
by alkylating phenol with copolymers of butylene and/or isobutylene
and/or propylene and one or more mono-olefinic comonomers
copolymerisable therewith (including for example ethylene,
1-pentene, 1-hexene, 1-octene, 1-decene and the like), for example
those in which the copolymer contains at least 50% by weight of
butylene and/or isobutylene and/or propylene units. The comonomers
may be aliphatic and can also contain non-aliphatic groups (for
example styrene, o-methylstyrene, p-methylstyrene, divinyl benzene
and the like). Suitable examples include polybutylphenols (for
example, formed by alkylating phenol with polybutylene), which
polybutylene includes for example, polymers made from pure or
substantially pure 1-butene or isobutene and mixtures made from
two, or all three of 1-butene, 2-butene and isobutene. High
reactivity polybutylenes are also suitable examples for making
suitable hydrocarbyl-substituted hydroxyaromatic compounds.
Examples of hydrocarbyl-substituted hydroxyaromatic compounds
include para-substituted hydroxyaromatic compounds. Examples of
hydrocarbyl-substituted hydroxyaromatic compounds include those
with one, two or more than two hydrocarbyl substituents.
[0098] Examples of suitable polyamine reactants (iii) include
alkylene polyamines for example containing a single reactive
primary or secondary amino group. Examples include those comprising
other groups including for example hydroxyl, cyano, amido and etc.
Examples of suitable polyamines include aliphatic diamines, for
example, those containing one primary or secondary amino group and
one tertiary amino group. Examples include
N,N,N'',N''-tetraalkyldialkylenetriamines;
N,N,N',N''-tetraalkyltrialkylenetetramines;
N,N,N',N'',N'''-pentaalkyltrialkylenetetramines;
N,N-dihydroxyalkyl-.alpha.,.omega.-alkylenediamines;
N,N,N'-trihydroxyalkyl-.alpha.,.omega.-alkylenediamines;
tris(dialkylaminoalkyl)aminoalkylmethanes etc. including those for
example, in which the alkyl groups are the same or different,
including those that typically contain no more than 12 carbon
atoms, for example 1 to 4 carbon atoms each e.g. methyl and/or
ethyl. Examples of polyamines containing one reactive primary or
secondary amino group that can participate in the Mannich
condensation reaction and at least one sterically hindered amino
group that cannot participate directly in the Mannich reaction
include for example, N-(tert-butyl)-1,3-propanediamine;
N-neopentyl-1,3-propranediamine;
N-(tert-butyl)-1-methyl-1,2-ethanediamine;
N-(tert-butyl)-1-methyl-1,3-propanediamine and
3,5-di(tert-butyl)aminoethylpiperazine.
[0099] Examples of suitable Mannich Base additives also include
those disclosed in, and/or obtained or obtainable by methods
described in U.S. Pat. No. 5,697,988. Thus, examples of suitable
Mannich Base additives include Mannich reaction products of (i) a
high molecular weight alkyl-substituted phenol, (ii) amine and
(iii) aldehyde wherein (i), (ii) and (iii) are reacted in a ratio
in the range of from 1.0:0.1-10.0:0.1-10. In at least some examples
the Mannich reaction products are obtained or obtainable by
condensing an alkyl-substituted hydroxyaromatic compound whose
alkyl-substituent has a number average molecular weight (Mn) in the
range of from 600 to 14000 for example polyalkylphenol whose
polyalkyl substituent is derived or derivable from 1-mono-olefin
polymers exhibiting a number average molecular weight in the range
of from 600 to 3000, for example in the range of from 750 to 1200;
an amine containing at least one >NH group, for example an
alkylene polyamine as represented by the formula:
H.sub.2N-(A-NH--).sub.xH in which A is a divalent alkylene group
containing 1 to 10 carbon atoms and x is an integer in the range of
from 1 to 10; and an aldehyde, for example formaldehyde in the
presence of a solvent. Suitable reaction conditions include one or
more of the following: [0100] operating at a temperature in the
range of from room temperature to 95.degree. C.; [0101] reacting
the compounds alone or in the presence of an easily removable
solvent for example benzene, xylene, toluene, or solvent refined
neutral oil; [0102] using formaldehyde (e.g. formalin) as the
aldehyde; [0103] heating the reaction mixture at an elevated
temperature (for example 120.degree. C. to 175.degree. C.) whilst
for example, blowing inert stripping gas (e.g. nitrogen, carbon
dioxide and the like) until dehydration is complete; and [0104]
filtering the reaction product and diluting with solvent.
[0105] Examples of Mannich reaction products include those derived
or derivable by reacting an alkylphenol, an ethylene polyamine and
a formaldehyde in respective molar ratio of 1.0:0.5-2.0:1.0-3.0
wherein the alky group of the alkyl phenol exhibits a number
average molecular weight (Mn) in the range of from 600 to 3000, for
example in the range of from 740 to 1200 or in the range of from
800 to 950 or for example 900. Examples of alkyl-substituted
hydroxyaromatic compounds include para-substituted
mono-alkylphenols and ortho mono-alkylphenols and dialkyl phenols.
Examples of amine reactants include polyamines, for example
polyethylene amines. Examples of amine reactants also include mono
and di-amino alkanes and their substituted analogs, for example
ethylamine, dimethylamine, dimethylaminopropyl amine and diethanol
amine; aromatic diamines, (e.g. phenylene diamine and diamine
naphthalenes); heterocyclic amines (e.g. morpholine, pyrrole,
pyrrolidine, imidazole, imidazolidine and piperidine); melamine;
and their substituted analogs. Examples of amine reactants include
alkylene polyamines, for example polyamines that are linear,
branched or cyclic; mixtures of linear and/or branched and/or
cyclic polyamines wherein each alkylene group contains from 1 to 10
carbon atoms, for example from 2 to 20 carbon atoms. Examples of
polyamines include those containing from 3 to 7 nitrogen atoms.
[0106] Examples of suitable Mannich Base additives also include
those disclosed in, and/or obtained or obtainable by methods
described in, U.S. Pat. No. 6,800,103. Thus, examples of suitable
Mannich Base additives include those obtained or obtainable by
reacting a mixture of (i) at least one substituted hydroxyaromatic
compound containing on the ring both (a) an aliphatic hydrocarbyl
substituent derived from a polyolefin exhibiting a number average
molecular weight in the range of 500 to 3000 and (b) a C.sub.1-4
alkyl; (ii) at least one secondary amine; and (iii) at least one
aldehyde. In at least some examples components (ii) and (iii) are
pre-reacted to from an intermediate prior to addition of component
(i). In at least some examples a mixture formed from components
(i), (ii) and (iii) is heated at a temperature above 40.degree. C.
at which Mannich condensation reaction takes place.
[0107] In at least some examples the Mannich reaction products is
obtained or obtainable by reacting a di-substituted hydroxyaromatic
compound in which the hydrocarbyl substituent (a) comprises
polypropylene, polybutylene or an ethylene alpha-olefin copolymer
exhibiting a number average molecular weight in the range of 500 to
3000 and a polydispersity in the range of 1 to 4, one or more
secondary amines and at least one aldehyde. In at least some
examples there is used dibutyl amine as the amine, formaldehyde or
formalin as the aldehyde and a molar ratio of the substituted
hydroxyaromatic compound to dibutyl amine to formaldehyde of
1:0.8-1.5:0.8-1.5 respectively, for example 1:0.9-1.2:0.9-1.2,
respectively.
[0108] Examples of representative di-substituted hydroxyaromatic
compounds include those represented by the general formula
(VII):
##STR00006##
[0109] in which each R is H, C.sub.1-4 alkyl or a hydrocarbyl
substituent exhibiting a number average molecular weight in the
range of 500 to 3000, with the proviso that one R is H, one R is a
C.sub.1-4 alkyl and one R is a hydrocarbyl substituent.
[0110] Examples of representative hydrocarbyl substituents of the
hydrocarbyl-substituted hydroxyaromatic compound (ii) include
polyolefin polymers for example polypropylene, polybutenes,
polyisobutylene, ethylene alpha-olefin copolymers and the like.
Other examples include copolymers of butylene and/or isobutylene
and/or propylene and one or more mono-olefinic comonomers
copolymerisable therewith (for example ethylene, 1-pentene,
1-hexene, 1-octene, 1-decene and the like) where the comonomer
molecule contains at least 50% by weight of butylene and/or
isobutylene and/or propylene units. In some examples the copolymers
are aliphatic and in some examples contain non-aliphatic groups
(for example styrene, o-methylstyrene, p-methylstyrene, divinyl
benzene and the like), in any case the resulting polymers are
substantially aliphatic hydrocarbon polymers. High reactivity
polybutylenes are also suitable for making suitable
hydrocarbyl-substituted hydroxyaromatic compounds.
[0111] Examples of suitable di-substituted hydroxyaromatic
compounds include those obtained or obtainable by alkylating
o-cresol with the high molecular weight polymers described
above.
[0112] Suitably in at least some examples, the hydrocarbyl
substituent is in the para-position of the disubstituted
hydroxyaromatic compound and the C.sub.1-4 alkyl substituent is in
the ortho-position.
[0113] Examples of representative secondary amines (ii) include
those represented by the general formula (VIII):
##STR00007##
[0114] in which R' and R'' are each independently alkyl,
cycloalkyl, aryl, alkaryl or aralkyl groups containing from 1 to 30
carbon atoms, for example 1 to 18 carbon atoms or 1 to 6 carbon
atoms. Examples include dimethylamine, diethylamine, dipropylamine,
dibutylamine, dipentylamine and dicyclohexylamine.
[0115] Examples of suitable Mannich Base additives also include
those disclosed in, and/or obtained or obtainable by methods
described in U.S. Pat. No. 7,597,726. Thus, examples of suitable
Mannich Base additives include Mannich condensation reaction
products of (i) a polyamine containing a sterically-hindered
primary amino group, (ii) a hydrocarbyl-substituted hydroxyaromatic
compound and (iii) and aldehyde. Examples of polyamines (i)
containing a sterically-hindered primary amino group include (A)
aliphatic cyclic polyamines containing a sterically-hindered
primary amino group, (B) acyclic aliphatic polyamines containing a
sterically-hindered primary amino group and combinations thereof.
In at least some examples the Mannich reaction product is obtained
or obtainable by reacting (1) 1,2-diaminocyclohexane, (2)
polyisobutylene-substituted cresol and/or phenol, and (3)
formaldehyde, for example in which the reactants (1), (2) and (3)
are reacted in equimolar proportions in a Mannich reaction. In at
least some examples the Mannich reaction product is dispersed in a
liquid carrier fluid. In at least some examples the polyamine
reactant contains an amino group that does not participate in the
Mannich condensation reaction with the hydrocarbyl-substituted
hydroxyaromatic reactant in addition to at least one reactive amino
group in the same polyamine molecule that takes part in the Mannich
reaction. Examples of reactive amino groups include primary and
secondary amino groups, for example non-sterically hindered
reactive primary amino groups. Examples of polyamines containing a
reactive amino group and a sterically-hindered amino group include
those represented by the formula (IX):
##STR00008##
wherein X and Z each is methylene, Y is an alkylene or
alkyleneamino group, n is 0 or 1, Q is an optional alkylene group
suitable for forming a ring structure with X and Z, E is a
hydrocarbyl group, t is 0 or 1, R.sup.1 is a hydrocarbyl group or
hydrogen provided that R.sup.1 is hydrocarbyl if n is 1, R.sup.2 is
hydrogen or a hydrocarbyl group, m is 0 or 1 provided that m is 0
if Q is present. If R.sup.1 and/or R.sup.2 is hydrocarbyl, examples
of such hydrocarbyl groups include C.sub.1 to C.sub.8 alkyl (for
example methyl, ethyl, propyl, isopropyl, t-butyl and the like).
Where n is 1, examples of Y include C.sub.1 to C.sub.8 alkylene;
alkyleneamino (for example methyleneamino, (--CH.sub.2N(H)--),
dimethyleneamino (--CH.sub.2N(H)--CH.sub.2--),
methyleneamino-ethylmethyleneamino
(--CH.sub.2N(H)--C.sub.2H.sub.4N(H)--CH.sub.2--) and the like).
Where t is 1, examples of E include methylene, ethylene,
isopropylene and the like. Examples of Q include alkylene chains,
for example C.sub.2-C.sub.4 alkylene chains. Examples of polyamines
containing a sterically hindered primary amino group include
aliphatic cyclic polyamines, including for example,
polyaminocycloalkanes, for example polyaminocyclohexanes, including
1,2-diaminodicyclohexanes, 1,3-diaminodicyclohexanes and
1,4-diaminodicyclohexanes, for example as represented by the
following formulae Xa, Xb and Xc:
##STR00009##
[0116] In at least some examples in the aliphatic cyclic polyamine
structure, a sterically hindering hydrocarbyl group generally is
bonded to the same carbon atom from which the sterically-hindered
primary amino group is bonded when the hindered/protected and
reactive amino groups are present in an arrangement other than an
ortho configuration relative to each other. In at least some
examples (for example compound Xc), a reactive amino group is
present as a moiety of an intervening substituent that is directly
attached to the ring structure. In at least some examples mixtures
of isomers are used. Examples of suitable acyclic aliphatic
polyamine reactants include alkylene polyamines containing a
primary amino group that is physically sterically-protected to
prevent or at least significantly hinder its ability to participate
in the Mannich condensation reaction. In at least some examples the
sterically hindered primary amino group is generally attached to
either a secondary or tertiary carbon atom in the polyamine
compound. The acyclic aliphatic polyamine has a suitably reactive
amino group (for example primary or secondary) in the same molecule
for participating in the Mannich condensation reaction. In at least
some examples other substituents are present, for example hydroxyl,
cyano, amido and the like. Examples of acyclic aliphatic polyamines
containing a sterically hindered primary amino group include those
represented by formulae XIa, XIb, XIc and XId:
##STR00010##
wherein each R.sub.1 and R.sub.2 are a hydrocarbyl group or a
hydrogen provided that at least one thereof is a hydrocarbyl group.
Examples of hydrocarbyl groups include C.sub.1 to C.sub.8 alkyl
e.g. methyl, ethyl, propryl, isopropyl and the like;
##STR00011##
[0117] Examples of hydrocarbyl-substituted hydroxyaromatic
compounds (ii) include those represented by formula XII:
##STR00012##
in which each R is H, C.sub.1-4 alkyl or a hydrocarbyl substituent
exhibiting an average molecular weight (Mw) in the range of 300 to
2000, for example 500 to 1500, for example as measured by gel
permeation chromatorgraphy, with the proviso that at least one R is
H and one R is a hydrocarbyl substituent as hereinbefore
defined.
[0118] Examples of representative hydrocarbyl substituents of the
hydrocarbyl-substituted hydroxyaromatic compound (ii) include
polyolefin polymers for example polypropylene, polybutenes,
polyisobutylene, ethylene alpha-olefin copolymers and the like.
Other examples include copolymers of butylene and/or isobutylene
and/or propylene and one or more mono-olefinic comonomers
copolymerisable therewith (for example ethylene, 1-pentene,
1-hexene, 1-octene, 1-decene and the like) where the comonomer
molecule contains at least 50% by weight of butylene and/or
isobutylene and/or propylene units. In some examples the copolymers
are aliphatic and in some examples contain non-aliphatic groups
(for example styrene, o-methylstyrene, p-methylstyrene, divinyl
benzene and the like), in any case the resulting polymers are
substantially aliphatic hydrocarbon polymers.
[0119] In at least some examples hydrocarbyl substituents include
polymers obtained or obtainable from pure or substantially pure
1-butene; polymers obtained or obtainable from pure or
substantially pure isobutene; and polymer obtained or obtainable
from mixtures of 1-butene, 2-butene and isobutene.
[0120] In at least some examples a suitable di-substituted
hydroxyaromatic compound is obtained or obtainable by alkylating
o-cresol with a high molecular weight hydrocarbyl polymer, for
example a hydrocarbyl polymer exhibiting an average molecular
weight in the range of from 300 to 2000, for example by alkylating
o-cresol or o-phenol with polyisobutylene exhibiting an average
molecular weight in the range of from 300 to 2000, for example in
the range of from 500 to 1500.
[0121] Examples of suitable Mannich Base additives also include
those disclosed in, and/or obtained or obtainable by methods
described in U.S.20090071065. Thus, examples of suitable Mannich
Base additives include Mannich condensation reaction products of:
(i) a polyamine having primary amino groups, (ii) a
hydrocarbyl-substituted hydroxyaromatic compound, and (iii) an
aldehyde, where the Mannich reaction is conducted at an overall
molar ratio of (i):(ii):(iii) such that, for example, the polyamine
(i) is reactable with the hydrocarbyl-substituted hydroxyaromatic
compound (ii) so as to obtain the substantially pure intermediate,
which intermediate is reactable with the aldehyde (iii) to obtain
the Mannich reaction product, for example in a one-pot reaction
process. Examples of polyamine (i) include 1,2-diaminocyclohexane,
1,3-diamino propane and 1,2-diamino ethane. Examples of suitable
molar ratios (i):(ii):(iii) include 1:2:3 and 1:1:2. Examples of
hydrocarbyl-substituted hydroxyaromatic compounds include those
represented by formula (XIII):
##STR00013##
[0122] in which each R is H, C.sub.1-4 alkyl, or a hydrocarbyl
substituent exhibiting an average molecular weight (Mw) in the
range of 300 to 2000, for example 500 to 1500, for example as
determined by gel permeation chromatography, with the proviso that
at least R is H and one R is a hydrocarbyl substituent as
hereinbefore defined. Examples of hydrocarbyl substituents include
polyolefin polymers, for example polypropylene, polybutylene,
polyisobutylene and ethylene alpha-olefin copolymers and also
copolymers of butylene and/or isobutylene and/or propylene and one
or more mono-olefinic comonomers copolymerisable therewith (for
example ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene and the
like) wherein the copolymer contains at least 50% by weight of
butylene and/or isobutylene and/or propylene units. Examples of
hydrocarbyl substituents include those obtained or obtainable from
polyisobutylene, for example polyisobutylene obtained or obtainable
from pure or substantially pure 1-butene or isobutene and polymers
obtained or obtainable from mixtures of two or three of 1-butene,
2-butene and isobutene. Examples of hydrocarbyl substituents
include those obtained or obtainable from high reactivity
polyisobutylene which have a relatively high proportion of polymer
having terminal vinylidene groups, for example at least 20%, 50% or
70% of the total terminal olefinic double bonds in the
polyisobutylene comprise an alkyl vinylidene isomer.
[0123] In at least some examples, more than one
hydrocarbyl-substituted aromatic compound is present/used. Where
more than one hydrocarbyl-substituted aromatic compound is
present/used, each hydrocarbyl-substituted aromatic compound may be
a Mannich base additive.
[0124] The hydrocarbyl-substituted aromatic compound is used in the
fuel composition at a concentration of actives in the range of from
about 20 ppm to about 200 ppm, such as from about 30 ppm to about
120 ppm. The hydrocarbyl-substituted aromatic compound is used in
the additive composition at a concentration of actives in the range
of from about 3% to about 25%, such as from about 5% to about 20%.
Concentration of actives means the concentration of the active
hydrocarbyl-substituted aromatic compound disregarding, for
example, any solvent and the like.
[0125] Typically, the hydrocarbyl-substituted aromatic compound
will be present/used in the fuel composition at a concentration of
actives of from about 20 ppm to about 70 ppm. In some examples,
however, higher treat rates may be used. In such instances, the
hydrocarbyl-substituted aromatic compound may be present/used in
the fuel composition at a concentration of from about 70 ppm to
about 200 ppm.
[0126] The polyalkylene amine may be used in the fuel composition
at a concentration of actives of from about 50 ppm to about 160 ppm
and the hydrocarbyl-substituted aromatic compound may be
present/used in the fuel composition at a concentration of actives
of from about 20 ppm to about 70 ppm. However, in some examples,
the polyalkylene amine may be present/used in the fuel composition
at a concentration of actives of from about 160 ppm to about 300
ppm and the hydrocarbyl-substituted aromatic compound may be
present/used in the fuel composition at a concentration of actives
of from about 70 ppm to about 200 ppm.
[0127] Where more than one hydrocarbyl-substituted aromatic
compound is present/used, the total concentration of the
hydrocarbyl-substituted aromatic compounds is as described
herein.
[0128] In at least some examples the weight ratio of actives of the
polyalkylene amine:the hydrocarbyl-substituted aromatic compound is
in the range of about 10:1 to about 1:10 for example about 5:1 to
about 1:5. In at least some examples, the weight ratio of actives
of the polyalkylene amine:the hydrocarbyl-substituted aromatic
compound is in the range of about 5:1 to about 1:1 for example
about 3.5:1 to about 1.5:1. Where more than one polyalkylene amine
and/or more than one hydrocarbyl-substituted aromatic compound is
present/used, the weight ratio of actives of all of the
polyalkylene amines:all of the hydrocarbyl-substituted aromatic
compound is as described herein.
[0129] Typically, the polyalkylene amine, contains a polyalkylene
group that exhibits a number average molecular weight of from about
700 to about 1500 (e.g. from about 800 to about 1200) and the
hydrocarbyl substituent of the hydrocarbyl-substituted aromatic
compound, which in some instances is or comprises polyisobutylene,
exhibits a number average molecular weight of from about 700 to
about 1500 (e.g. about 900 to about 1300).
Carrier Fluid.
[0130] In at least some examples, a carrier fluid (sometimes also
called induction aid or fluidiser) is present/used in the additive
composition and/or the fuel composition. In at least some examples
more than one carrier fluid is present/used.
[0131] In at least some examples the carrier fluid is provided with
the polyalkylene amine. In at least some examples the carrier fluid
is provided with the hydrocarbyl-substituted aromatic compound. In
at least some examples a carrier fluid is provided with each of the
polyalkylene amine and the hydrocarbyl-substituted aromatic
compound, which carrier fluids may be the same or different. In at
least some examples the carrier fluid is provided independently of
the polyalkylene amine and the hydrocarbyl-substituted aromatic
compound.
[0132] Examples of suitable carrier fluids are described for
example in U.S.2009/0071065 at paragraphs [0038] to [0053]. Thus,
examples of suitable carrier fluid include liquid poly-alpha olefin
oligomers, liquid polyalkene hydrocarbons (for example
polypropylene, polybutenes, polyisobutene and the like), liquid
hydrotreated polyalkene hydrocarbons (for example hydrotreated
polypropylene, hydrotreated polybutenes, hydrotreated polyisobutene
and the like), mineral oils, liquid poly(oxyalkylene) compounds,
liquid alcohols, liquid polyols, liquid esters and the like.
[0133] Examples of carrier fluids include (1) a mineral oil or
blend of mineral oils, for example those exhibiting a viscosity
index of less than 120; (2) one or a blend of poly alpha olefins,
for example those exhibiting an average molecular weight in the
range of from 500 to 1500; (3) polyethers including
poly(oxyalkylene) compounds, for example those exhibiting an
average molecular weight in the range of from 500 to 1500; (4) one
or more liquid polyalkylenes; and (5) mixtures of two or more
selected from the group consisting of (1), (2), (3) and (4).
[0134] Examples of suitable mineral oil carrier fluids include
paraffinic, naphthenic and asphaltic oils, for example hydrotreated
oils. Examples of mineral oils exhibit a viscosity at 40.degree. C.
of less than 1600 SUS, for example 300 to 1500 SUS and/or exhibit a
viscosity index of less than 100, for example in the range 30 to
60.
[0135] Examples of suitable poly alpha olefin carrier fluids
include hydrotreated and unhydrotreated poly alpha olefins.
Examples of poly alpha olefins include trimmers, tetramers and
pentamers of alpha olefin monomers containing 6 to 12 carbon
atoms.
[0136] Examples of suitable polyether carrier fluids include
poly(oxyalkylene) compounds exhibiting an average molecular weight
in the range of from 500 to 1500, including for example
hydrocarbyl-terminated poly(oxyalkylene) monols. Examples of
poly(oxyalkylene) compounds include one or a mixture of
alkylpoly(oxyalkylene)monols which in its undiluted state is a
gasoline-soluble liquid exhibiting a viscosity of at least 70 cSt
at 40.degree. C. and at least 13 cSt at 100.degree. C., including
such monols formed by propoxylation of one or a mixture of alkanols
containing at least 8 carbon atoms, for example 10 to 18 carbon
atoms.
[0137] Examples of suitable poly(oxyalkylene) carrier fluids
include those exhibiting a viscosity in the undiluted state of at
least 60 cSt at 40.degree. C. (for example at least 70 cSt at
40.degree. C.) and at least 11 cSt at 100.degree. C. (for example
at least at least 13 cSt at 100.degree. C.). Examples of suitable
poly(oxyalkylene) carrier fluids include those exhibiting
viscosities in their undiluted state of no more than 400 cSt at
40.degree. C. (for example no more than 300 cSt at 40.degree. C.)
and no more than 50 cSt at 100.degree. C. (for example no more than
40 cSt at 100.degree. C.).
[0138] Examples of poly(oxyalkylene) compounds include
poly(oxyalkylene) glycol compounds and monoether derivatives
thereof, for example those that satisfy the above viscosity
requirements, including those that are obtained or obtainable by
reacting an alcohol or polyalcohol with an alkylene oxide, for
example propylene oxide and/or butylene oxide with or without the
use of ethylene oxide, for example products in which at least 80
mol. % of the oxyalkylene groups in the molecule are derived or
derivable from 1,2-propylene groups.
[0139] Examples of poly(oxyalkylene) compounds include those
disclosed in, and/or obtained or obtainable by methods described
in, U.S. Pat. No. 248,664, U.S. Pat. No. 2,425,845, U.S. Pat. No.
2,425,755 and U.S. Pat. No. 2,457,139.
[0140] The poly(oxyalkylene) carrier compounds should contain
sufficient branched oxyalkylene units (for example
methyldimethyleneoxy units and/or ethyldimethyleneoxy units) to
render the poly(oxyalkylene) compound gasoline soluble.
[0141] Examples of polyalkylene carrier fluids include
polypropenes, polybutenes, polyisobutenes, polyamylenes, copolymers
of propene and butene, copolymers of butene and isobutene,
copolymers of propene and isobutene and copolymers of propene,
butene and isobutene and mixtures thereof.
[0142] Examples of polyalkylene carrier fluids also include
hydrotreated polypropylenes, hydrotreated polybutenes, hydrotreated
polyisobutenes and the like.
[0143] Examples of polybutenes carrier fluids include those
exhibiting a narrow molecular weight distribution, for example as
expressed as the ratio Mw/Mn that is, (mass average molecular
mass)/(the number average molecular mass), this ratio is sometimes
called the polydispersity index. Examples of polybutenes carrier
fluids include those exhibiting a narrow molecular weight
distribution, expressed as the ratio Mw (mass average molecular
mass)/Mn the number average molecular mass of 1.4 or less, for
example as described in U.S. Pat. No. 6,048,373. Methods of
determining mass average molecular mass include static light
scattering, small angle neutron scattering, X-ray scattering, and
sedimentation velocity. Number average molecular mass or weight
(Mn) can be determined by gel permeation chromatography.
[0144] The carrier fluid is preferably a polyether carrier fluid,
such as a polyalkylene glycol. Polyethylene glycol, polypropylene
glycol and block co-polymers thereof may be used.
[0145] The carrier fluid may be used in the additive composition in
an amount of about 1% to about 50% by weight, such as about 5% to
about 25% by weight, preferably about 10% to about 20% by weight.
The carrier fluid may be used in the fuel composition in an amount
of about 5 ppm to about 1000 ppm, such as about 20 ppm to about 300
ppm, preferably about 35 ppm to about 200 ppm.
[0146] Where more than one carrier fluid is present/used, the total
concentration of the carrier fluid is as described herein.
Fuel Composition
[0147] The fuel composition is suitable for use for example, in a
spark ignition internal combustion engine or a compression-ignition
gasoline internal combustion engine.
[0148] In at least some examples the fuel composition has a sulphur
content of up to 50.0 ppm by weight, for example up to 10.0 ppm by
weight.
[0149] Examples of suitable fuel compositions include leaded and
unleaded fuel compositions.
[0150] In at least some examples the fuel composition meets the
requirements of EN 228, for example as set out in BS EN 228:2012.
In at least some examples the fuel composition meets the
requirements of ASTM D 4814-14.
[0151] In at least some examples the fuel composition for
spark-ignition internal combustion engines exhibits one or more
(for example all) of the following, for example, as defined
according to BS EN 228:2012 :- a minimum research octane number of
95.0, a minimum motor octane number of 85.0 a maximum lead content
of 5.0 mg/l, a density of 720.0 to 775.0 kg/m.sup.3, an oxidation
stability of at least 360 minutes, a maximum existent gum content
(solvent washed) of 5 mg/100 ml, a class 1 copper strip corrosion
(3 h at 50.degree. C.), clear and bright appearance, a maximum
olefin content of 18.0% by weight, a maximum aromatics content of
35.0% by weight, and a maximum benzene content of 1.00% by
volume.
[0152] Examples of suitable fuel compositions include for example
hydrocarbon fuels, oxygenate fuels and combinations thereof.
[0153] Hydrocarbon fuels may be derived from mineral sources and/or
from renewable sources such as biomass (e.g. biomass-to-liquid
sources) and/or from gas-to-liquid sources and/or from
coal-to-liquid sources.
[0154] Examples of suitable oxygenate fuel components in the fuel
composition include straight and/or branched chain alkyl alcohols
having from 1 to 6 carbon atoms, for example methanol, ethanol,
n-propanol, n-butanol, isobutanol, tert-butanol. Suitable oxygenate
components in the fuel composition for spark-ignition internal
combustion engines include ethers, for example having 5 or more
carbon atoms, for example methyl tert-butyl ether and ethyl
tert-butyl ether. In at least some examples the fuel composition
has a maximum oxygen content of 2.7% by mass. In at least some
examples fuel composition has maximum amounts of oxygenates as
specified in EN 228, for example methanol: 3.0% by volume, ethanol:
5.0% by volume, iso-propanol: 10.0% by volume, iso-butyl alcohol:
10.0% by volume, tert-butanol: 7.0% by volume, ethers (for example
having 5 or more carbon atoms): 10% by volume and other oxygenates
(subject to suitable final boiling point): 10.0% by volume. In at
least some examples fuel composition comprises ethanol complying
with EN 15376 at a concentration of up to 15% by volume, for
example up to 10% by volume or up to 5.0% by volume. Examples of
oxygenate-containing fuel compositions include E5, E10, E15 and
fuel compositions containing ethanol at higher concentrations, for
example up to E85.
[0155] According to an aspect of the present invention the additive
composition which comprises: [0156] a. a hydrocarbyl-substituted
aromatic compound; and [0157] b. a polyalkylene amine is
incorporated, in one or more steps, into a fuel composition for use
in a spark-ignition internal combustion engine.
[0158] In at least some examples, the hydrocarbyl-substituted
aromatic compound and the polyalkylene amine are incorporated into
the fuel composition separately or together as components of one or
more additive concentrates, one or more additive packages and/or
one or more additive part packs.
Further Additives
[0159] In at least some examples the fuel compositions and/or
additive compositions comprise at least one other fuel
additive.
[0160] In at least some examples the additives are admixed and/or
incorporated as one or more additive concentrates and/or additive
part packs, optionally comprising solvent or diluent.
[0161] In at least some examples, the fuel composition is prepared
by admixing in one or more steps, one or more base fuels (for
example hydrocarbon fuels, oxygenate fuels and combinations
thereof) and components therefor, optionally with one or more
additives and/or part additive package concentrates. In at least
some examples, the additives, additive concentrates and/or part
additive package concentrates are admixed with the fuel or
components therefor in one or more steps.
[0162] Examples of such other additives that may be present in the
additive compositions and the fuel compositions of the present
invention include friction modifiers, anti-wear additives,
corrosion inhibitors, dehazers/demulsifiers, dyes, markers,
odorants, octane improvers, combustion modifiers, anti-oxidants,
anti-microbial agents, lubricity improvers and valve seat recession
additives. In particular, demulsifiers and corrosion inhibitors may
be used in the additive composition and the fuel composition.
[0163] Representative suitable and more suitable independent
amounts of additives (if present) and solvent in the fuel
composition are given in Table 1. For the additives, the
concentrations expressed in Table 1 are by weight of active
additive compounds that is, independent of any solvent or
diluent.
[0164] In at least some examples, more than one of each type of
additive is present. In at least some examples, within each type of
additive, more than one class of that type of additive is present.
In at least some examples more than one additive of each class of
additive is present. In at least some examples additives are
suitably supplied by manufacturers and/or suppliers in solvent or
diluents. Where more than one of each type of additive is present,
the total amount of each type of additive is expressed in Table
1.
TABLE-US-00001 TABLE 1 Fuel Composition Additive Composition More
suitable More suitable Suitable amount Suitable amount amount
(actives), if amount (actives), if (actives), (by present
(actives), (by present weight) (by weight) weight) (by weight)
Hydrocarbyl-substituted 20-200 ppm 30-120 ppm 3-25% 5-20% aromatic
compounds Polyalkylene amines 50-300 ppm 70-250 ppm 5-55% 10-50%
Carrier fluid 20-300 ppm 35-200 ppm 5-25% 10-20%
Dehazers/demulsifiers 0.05-30 ppm 0.1-10 ppm 0-5% 0.01-2% Corrosion
inhibitors 0.1-100 ppm 0.5-40 ppm 0-10% 0.1-5% Other additive 0-500
ppm 0-200 ppm 0-30% 0-15% components Solvent 10-3000 ppm 50-1000
ppm 10-75% 20-65%
[0165] In examples, the additive composition consists of additives
and solvents as recited in Table 1.
[0166] Other additive components include friction
modifiers/anti-wear additive, dyes and/or fuel markers, octane
improvers and/or combustion improvers, anti-oxidants, odorants,
anti-microbial agents and lubricity improvers.
[0167] Examples of suitable friction modifiers and anti-wear
additives include those that are ash-producing additives or ashless
additives. Examples of friction modifiers and anti-wear additives
include esters (for example glycerol mono-oleate) and fatty acids
(for example oleic acid and stearic acid).
[0168] Examples of suitable corrosion inhibitors include ammonium
salts of organic carboxylic acids, amines and heterocyclic
aromatics, for example alkylamines, imidazolines and
tolyltriazoles.
[0169] Examples of suitable non-metallic octane improvers include
N-methyl aniline.
[0170] Examples of suitable metal-containing octane improvers
include methylcyclopentadienyl manganese tricarbonyl, ferrocene and
tetra-ethyl lead. Suitably, the fuel composition is free of all
added metallic octane improvers including methyl cyclopentadienyl
manganese tricarbonyl and other metallic octane improvers including
for example, ferrocene and tetraethyl lead.
[0171] In examples, nitrogen-based ashless octane improvers are
present in the additive compositions and the fuel compositions.
These compounds improve the octane rating of the fuel, but reduce
performance in other areas of the engine. The use of a polyalkylene
amine and a hydrocarbyl-substituted aromatic compound in the
additive compositions an fuel compositions of the present invention
may help to prevent reductions in performance in the engine caused
by nitrogen-based ashless octane improvers.
[0172] Examples of suitable anti-oxidants include phenolic
anti-oxidants (for example 2,4-di-tert-butylphenol and
3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) and aminic
anti-oxidants (for example para-phenylenediamine, dicyclohexylamine
and derivatives thereof).
[0173] Examples of suitable valve seat recession additives include
inorganic salts of potassium or phosphorus.
[0174] In at least some examples the additive composition comprises
solvent. Examples of suitable solvents include polyethers and
aromatic and/or aliphatic hydrocarbons, for example heavy naphtha
e.g. Solvesso (Trade mark), xylenes and kerosene.
[0175] In at least some examples the additives are present in the
fuel composition at a total amount in the range of 20 to 25000 ppm
by weight. Therefore, the concentrations of each additive in an
additive concentrate will be correspondingly higher than in the
fuel composition, for example by a ratio of 1:0.00002 to 0.025. In
at least some examples the additives are used as part-packs, for
example part of the additives (sometimes called refinery additives)
being added at the refinery during manufacture of a fungible fuel
and part of the additives (sometimes called terminal or marketing
additives) being added at a terminal or distribution point.
[0176] In at least some examples the hydrocarbyl-substituted
aromatic compound and the polyalkylene amine are incorporated or
admixed with other components of the fuel composition as a refinery
additive composition or as a marketing additive composition.
[0177] In at least some examples the hydrocarbyl-substituted
aromatic compound and the polyalkylene amine are incorporated or
admixed with other components of the fuel composition as a
marketing additive, for example at a terminal or distribution
point.
[0178] The hydrocarbyl-substituted aromatic compound and the
polyalkylene amine may be incorporated or admixed with other
components of the additive composition for sale in a bottle, for
addition to fuel at a later time.
[0179] The fuel compositions may be for use in a port fuel
injection internal combustion engine or a direct injection internal
combustion engine.
[0180] Examples of suitable direct injection spark-ignition
internal combustion engines include boosted direct injection
spark-ignition internal combustion engines, for example
turbocharged boosted direct injection engines and supercharged
boosted direct injection engines. Suitable engines include 2.0L
boosted direct injection spark-ignition internal combustion
engines. Suitable direct injection engines include those that have
side mounted direct injectors and/or centrally mounted direct
injectors.
[0181] Examples of suitable port fuel injection, spark-ignition
internal combustion engines include any suitable port fuel
injection, spark-ignition internal combustion engine including for
example BMW 318i engine, Ford 2.3L Ranger engine and MB M111
engine.
[0182] Methods of measuring the port fuel injection intake valve
deposit clean-up performance of a fuel composition for use in a
port fuel injection, spark-ignition internal combustion engine
include those according to (or at least based on) US industry
standard test method: ASTM D-6201 (version 04, 2009), this is
sometimes also called the Ford 2.3L "Ranger" engine test after the
engine that is used. Methods for assessing the deposits on the port
fuel injection intake valves include weighing and/or assigning
numerical ratings by visual inspection by trained technicians.
[0183] Methods for assessing the enhanced direct injection air
intake valve deposit performance when the fuel composition is used
to operate a direct injection spark-ignition internal combustion
engine include assessing the deposits on the valves by weighing
and/or by assigning numerical ratings by visual inspection by
trained technicians, for example according to ASTM D-6201 (e.g.
version 04, 2009). In at least some examples determination of air
intake valve deposits takes place after operating the
spark-ignition internal combustion engine under conditions to
induce blow-by flow into the engine inlet system just upstream of
the air intake valves, for example by operating a four-stage test
cycle of steady-state stages running at engine speeds of between
1000 and 2000 rpm and with engine loads of between 1 and 5 bar
Brake Mean Effective Pressure for a total duration of greater than
100 hours.
[0184] The fuel compositions control direct injection intake valve
deposits, but it is desirable that they also exhibit good
detergency in the rest of the engine. This may be determined by
measuring the port fuel injection intake valve deposit performance
of the fuel composition in a spark-ignition internal combustion
engine, such as by using the industry standard test method:
CEC-F-20-A-98, also known as the M111 test. Other methods include
assessing the deposits that form on the direct injectors by
carrying out static injector flow tests.
[0185] Methods for assessing the sludge and piston vanish control
performance of a fuel composition include those based upon the US
industry standard test method: ASTM D-6593 (version 10), this is
sometimes also called the Ford 4.6L "Sequence VG" engine test.
Though this test is typically used for determining the performance
of lubricants, it can also be used to test the performance of fuels
by using the standard reference lubricant as the lubricant, and the
standard reference base fuel with the additives of interest added
thereto as the fuel.
[0186] The fuel compositions control sludge and piston varnish
formation, but it is desirable that they also exhibit good
detergency in the rest of the engine, for instance on an intake
valve. This may be determined by measuring intake valve keep-clean
performance of the fuel composition. Methods of measuring the
intake valve deposit keep-clean performance of a fuel composition
for use in a spark-ignition internal combustion engine include
those based upon the US industry standard test method: ASTM D-6201
(version 04, 2009).
[0187] Particulate emissions may be measured by assessing the
number of particles emitted from an engine. Methods for assessing
the number of particles emitted from an engine include those in
which a Condensation Particle Counter is fitted to an engine. The
Condensation Particle Counter preferably measures the concentration
of particles with a size in the range of from 23 nm to 2.5 .mu.m.
The Condensation Particle Counter preferably meets the legislative
requirements of the European Commission's Particle Measurement
Programme (PMP). A turbocharged boosted direct injection
spark-ignition internal combustion engine (2.0 litre or less) may
be used. The engine may be run for more than 12 hours, such as for
more than 15 hours. The engine may be run at single load point,
preferably representative of real-world engine operation such as
motorway driving operation.
[0188] The fuel compositions control particulate emissions, but it
is desirable that they also exhibit good detergency in the rest of
the engine. This may be determined by measuring the intake valve
deposit keep-clean performance of the fuel composition in a
spark-ignition internal combustion engine, such as by using the
industry standard test method: CEC-F-20-A-98, also known as the
M111 test.
[0189] Further aspects of the present invention include the
aspects, embodiments, instances and examples defined above but in
which a Mannich Base additive is used as component a. In these
aspects, the Mannich Base additive may be, but does not have to be,
a hydrocarbyl-substituted aromatic compound.
[0190] The invention will now be described with reference to the
following non-limiting examples.
[0191] In the drawings FIGS. 1 and 2 represent in graph form
clean-up performance versus additive treat rate (concentration) for
the fuel compositions tested.
EXAMPLE 1
PFI Inlet Valve Clean-Up
[0192] Port fuel intake valve deposit (PFI IVD) "clean-up" and
"keep-clean" performance were assessed using the US industry
standard test method: ASTM D-6201 (also known as the Ford 2.3L
"Ranger" engine test) using a Ford 2.3 L port fuel injection
spark-ignition internal combustion engine. The ASTM D-6201 cycle is
as shown in Table 2.
TABLE-US-00002 TABLE 2 Manifold Absolute Pressure Engine speed
(engine load requirement) Duration Stage rpm kPa mm Hg minutes Ramp
from 0 to (Transition) (Transition) (Transition) 0.5 2000 rpm
Steady state 2000 30.6 230 4 Ramp from 2000 (Transition)
(Transition) (Transition) 0.5 to 2800 rpm Steady state 2800 71.8
540 8
[0193] The engine was operated continuously according to the test
cycle in Table 2 for a "dirty-up" period using a US market-regular
gasoline to produce at least 400 mg deposit per valve. Then the
engine was operated continuously according to the test cycle in
Table 2 for a clean-up test period of 100 hours using the test fuel
composition. Each port fuel intake valve was weighed at the start
of the evaluation, after the interim "dirty-up" period and at the
end of the evaluation. "Clean-up" was calculated for each valve as:
100.times.[(Interim valve weight)-(End of Test valve
weight)]/[(Interim valve weight)-(Start of Test valve weight ]. An
average of the values for the four valves was reported. The higher
the result (higher % "clean-up") the better the performance.
[0194] The clean-up evaluation was assessed using two different
formulated E10 gasolines (referred to as E10a and E10b) containing
either a PIBA additive or a combination of a PIBA additive and a
Mannich Base. Different total treat rates of the PIBA or PIBA and
Mannich combination were used. The data are shown in Tables 3 and
4.
TABLE-US-00003 TABLE 3 Clean up Concentration (% relative to
(arbitrary units: clean-up of mass/volume) Experiment A) PIBA
(E10a) - Experiment A 3.52 100 PIBA (E10a) 5.70 204 PIBA and
Mannich Base (E10a) 2.88 120 PIBA and Mannich Base (E10a) 3.57 138
PIBA and Mannich Base (E10a) 4.47 199 *a high number indicates
better clean-up performance
TABLE-US-00004 TABLE 4 Clean up Concentration (% relative to
(arbitrary units: clean-up of mass/volume) Experiment B) PIBA
(E10b) - Experiment B 3.52 100 PIBA (E10b) 5.70 137 PIBA and
Mannich Base (E10b) 2.6 71 PIBA and Mannich Base (E10b) 2.88 62
PIBA and Mannich Base (E10b) 4.47 107 *a high number indicates
better clean-up performance
[0195] The data in Tables 3 and 4 show that the fuel composition
comprising in combination, at least one Mannich Base additive and
at least one polyisobutylene amine exhibits beneficial port fuel
injection intake valve deposit clean-up performance when used in a
port fuel injection, spark-ignition internal combustion engine and
in particular exhibits a beneficially steep gradient for
performance versus treat rate response. This performance versus
treat rate response can be seen in FIGS. 1 and 2.
EXAMPLE 2
DI Intake Valve Deposits Keep-Clean
[0196] Air intake valve deposit formation was studied using a
gasoline base fuel meeting E0 R95 EN 228 specifications. Fuels were
prepared with and without deposit controlling additives, and used
to operate a 2.0 litre turbocharged direct injection spark ignition
internal combustion engine. The engine was operated to induce
blow-by flow into the engine inlet system just upstream of the air
intake valves by operating a four-stage test cycle of steady-state
stages running at engine speeds of between 1000 and 2000 rpm and
with engine loads of between 1 and 5 bar Brake Mean Effective
Pressure for a total duration of greater than 100 hours. The amount
of PIBA additive or combined PIBA additive and Mannich Base
additive used in the experiments was selected to give a typical
port fuel injection intake valve deposit performance when measured
using an M111 spark ignition internal combustion engine operated
according to the industry standard test CEC-F-20-A-98. The mass of
air intake valve deposits were determined by weighing the valves at
the start and end of each test and subtracting the weight at the
start from the weight at the end. The results are shown in Table
5.
TABLE-US-00005 TABLE 5 Air Intake Valve Deposits in DI
spark-ignition engine Additive(s) (mass % relative to Experiment C)
None (three repeat experiments) 100 - Experiment C 96 101
Polyisobutylene amine (two repeat 121 experiments) 122 Mannich Base
Additive (I) and 105 Polyisobutylene Amine Two Mannich Additives (I
and II) 131 Mannich Additive (II) 116 Mannich Additive (III) 107 *a
low number indicates better keep-clean performance
[0197] The results in Table 5 show that incorporating into a fuel,
a combination of Mannich Base additive and polyisobutylene amine
reduces the direct injection air intake valve deposit forming
tendency of the fuel composition when used in a direct injection
spark-ignition internal combustion engine.
[0198] In a further experiment, the different fuel compositions
were run on a 2.0 litre direct injection spark ignition internal
combustion engine. Injector flow loss from each test was measured
using static injector flow tests to confirm that the detergency
effects of the different fuel compositions on the direct injectors
were comparable.
EXAMPLE 3
Piston Varnish and Sludge Formation Keep-Clean
[0199] Intake valve deposit (IVD) keep-clean performance were
assessed using the US industry standard test method: ASTM D-6201
(version 04, 2009) using a Ford 2.3 L port fuel injection
spark-ignition internal combustion engine. Intake valve deposit
(IVD) keep-clean performance was studied using an E10 gasoline base
fuel. Sludge (engine sludge and rocker cover sludge) formation and
piston varnish formation were assessed using the US industry
standard test method: ASTM D-6593 (version 20100628) using a Ford
4.6L port fuel injection spark-ignition internal combustion engine.
The standard reference fuel in ASTM D-6593, with additives of
interest added therein, was used as the fuel, and the standard
reference lubricant in ASTM D-6593 was used as the lubricant in the
engine. The amount of additive used in the sludge and piston
varnish formation tests was selected to give a typical port fuel
injection valve keep-clean performance. The data are shown in Table
6.
TABLE-US-00006 TABLE 6 Engine sludge control performance Keep-clean
Treat rate (% relative to base Piston varnish deposit performance
(arbitrary fuel reference)* control performance (arbitrary units
mass Rocker (% relative to base units) per volume) Engine cover
fuel reference)* PIBA 10.0 20.0 113% 100% 106% PIBA and 9.9 18.9
115% 103% 115% Mannich *a high number indicates better control
performance
[0200] The data generated demonstrate that the fuel composition
comprising Mannich Base additive in combination with a
polyisobutylene amine exhibits beneficial sludge and piston varnish
formation control in a spark-ignition internal combustion
engine:
EXAMPLE 4
Particulate Emissions
[0201] Particulate emissions were measured by assessing the number
of particles emitted using a Condensation Particle Counter fitted
to a 1.6 litre turbocharged direct-injection spark ignition
internal engine. The Condensation Particle Counter meets the
legislative requirements of the European Commission's PMP. The
number of particles that were emitted from the engine was assessed
after the engine had been running for 15 hours. The fuel that was
used to determine the intake valve deposit keep-clean performance
was splash blended with ethanol to form an Ell) gasoline base fuel
for use in the engine tests. The amount of Mannich Base additive
used in the experiment was selected to give a typical port fuel
injection valve clean-up performance using the industry standard
test method: CEC-F-20-A-98 (Issue 12). An E0 gasoline base fuel
with a Research Octane Number of 95 was used. The fuel was EN 228
compliant. The data are shown in Table 7.
TABLE-US-00007 TABLE 7 15 hour particle number emissions Additives
(arbitrary units) None 7.7 Mannich Additive 10.1 Two Mannich
Additives 10.9 PIBA 5.2 Mannich Additive and PIBA 1.6 *a low number
indicates particle number control performance
[0202] The data shown in Table 7 demonstrates that the fuel
composition comprising a Mannich Base additive in combination with
a polyisobutylene amine exhibits beneficial particulate emissions
control in a direct-injection spark-ignition internal combustion
engine.
[0203] Tests to determine the increase in injector pulse width over
the 15 hour test cycle were also carried out, and demonstrate that
a fuel compositions containing a Mannich Base additive and PIBA
additive exhibits comparable injector pulse width increase control
to a fuel composition which contains only PIBA additive. Increase
in injector pulse width may be used as a measure of the detergency
of fuel compositions.
[0204] These data illustrate that the fuel compositions of the
present invention are able to exhibit a number of beneficial
effects in different engines. In particular, the data show that,
when used in a spark-ignition internal combustion engine, the
additive composition controls sludge formation and piston varnish
formation. The data also show that, when used in a direct injection
spark-ignition internal combustion engine, the additive composition
controls particulate emission and deposit formation on intake
valves. The data also show that, when used in a port fuel injection
spark-ignition internal combustion engine, the additive composition
reduces the port fuel injection valve deposits.
* * * * *