U.S. patent application number 15/510480 was filed with the patent office on 2017-09-07 for methods and uses of controlling particulate emissions in an internal combustion engine.
This patent application is currently assigned to BP OIL INTERNATIONAL LIMITED. The applicant listed for this patent is BP OIL INTERNATIONAL LIMITED. Invention is credited to Robert Edward ALLAN, Timothy Hugh LAKE, Charmaine NATHANIEL, David Michael WILLIAMSON.
Application Number | 20170253820 15/510480 |
Document ID | / |
Family ID | 51869461 |
Filed Date | 2017-09-07 |
United States Patent
Application |
20170253820 |
Kind Code |
A1 |
ALLAN; Robert Edward ; et
al. |
September 7, 2017 |
METHODS AND USES OF CONTROLLING PARTICULATE EMISSIONS IN AN
INTERNAL COMBUSTION ENGINE
Abstract
The use as a particulate emissions and/or a complex
poly-aromatic nuclei (CPAN) controlling additive in a fuel
composition for a direct-injection spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine of a combination of: a. a hydrocarbyl-substituted
aromatic compound; and b. a polyalkylene amine.
Inventors: |
ALLAN; Robert Edward;
(Middlesex, GB) ; LAKE; Timothy Hugh; (Middlesex,
GB) ; NATHANIEL; Charmaine; (Middlesex, GB) ;
WILLIAMSON; David Michael; (Middlesex, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BP OIL INTERNATIONAL LIMITED |
Middlesex |
|
GB |
|
|
Assignee: |
BP OIL INTERNATIONAL
LIMITED
Middlesex
GB
|
Family ID: |
51869461 |
Appl. No.: |
15/510480 |
Filed: |
September 10, 2015 |
PCT Filed: |
September 10, 2015 |
PCT NO: |
PCT/EP2015/070691 |
371 Date: |
March 10, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 10/08 20130101;
C10L 2200/0423 20130101; C10L 10/02 20130101; C10L 1/22 20130101;
C10L 1/221 20130101; C10L 10/18 20130101; C10L 2270/023 20130101;
C10L 2200/0446 20130101; C10L 2230/22 20130101; C10L 1/236
20130101; C10L 2270/026 20130101; C10L 1/238 20130101; C10L 1/2383
20130101 |
International
Class: |
C10L 10/02 20060101
C10L010/02; C10L 10/08 20060101 C10L010/08; C10L 10/18 20060101
C10L010/18; C10L 1/22 20060101 C10L001/22 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 11, 2014 |
GB |
1416082.4 |
Claims
1-17. (canceled)
18. A method of controlling particulate emissions from a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine which
method comprises supplying to the engine a fuel composition which
comprises a combination of: a. a hydrocarbyl-substituted aromatic
compound; and b. a polyalkylene amine, the hydrocarbyl-substituted
aromatic compound and the polyalkylene amine being present in the
fuel composition in an amount such that substantially less
particulate emissions are formed when the fuel composition is
combusted in the engine than when the same fuel composition without
the combination of the hydrocarbyl-substituted aromatic compound
and the polyalkylene amine is combusted in the engine.
19. The method of claim 18, wherein the hydrocarbyl-substituted
aromatic compound is a Mannich Base additive.
20. The method of claim 18, wherein the polyalkylene amine is a
polyisobutylene amine.
21. The method of claim 18, wherein the hydrocarbyl-substituted
aromatic compound is present in the fuel composition at a
concentration of actives of from about 20 ppm to about 300 ppm.
22. The method of claim 18, wherein the hydrocarbyl substituent of
the aromatic compound exhibits a number average molecular weight of
from about 700 to about 1500.
23. The method of claim 18, wherein the hydrocarbyl substituent of
the aromatic compound is or comprises polyisobutylene.
24. The method of claim 18, wherein the polyalkylene amine is
present in the fuel composition at a concentration of actives of
from about 50 ppm to about 500 ppm.
25. The method of claim 18, wherein the polyalkylene amine contains
a polyalkylene group that exhibits a number average molecular
weight of from about 700 to about 1500.
26. The method of claim 18, wherein the weight ratio of actives of
the polyalkylene amine:the hydrocarbyl-substituted aromatic
compound in the fuel composition is in the range of from about 5:1
to about 1:5.
27. The method of claim 18, wherein the engine is a spark-ignition
internal combustion engine.
28. The method of claim 18, wherein the engine is a
compression-ignition gasoline internal combustion engine.
29. The method of claim 18, wherein the at least one polyalkylene
amine is present in the fuel composition at a concentration of
actives of from 100 ppm to 500 ppm.
30. The method of claim 18, wherein the at least one polyalkylene
amine is present in the fuel composition at a concentration of
actives of from 160 ppm to 500 ppm.
31. The method of claim 18, wherein the at least one
hydrocarbyl-substituted aromatic compound is present in the fuel
composition at a concentration of actives of from 70 ppm to 200
ppm.
32. The method of claim 18, wherein the at least one
hydrocarbyl-substituted aromatic compound is present in the fuel
composition at a concentration of actives of from 70 ppm to 200
ppm; and the at least one polyalkylene amine is present in the fuel
composition at a concentration of actives of from 160 ppm to 500
ppm.
33. The method of claim 18, wherein the hydrocarbyl-substituted
aromatic compound is a Mannich Base additive, and the polyalkylene
amine is a polyisobutylene amine.
34. A method of reducing the particulate emitting tendency of a
fuel composition for use in a direct-injection spark-ignition
internal combustion engine or a compression-ignition gasoline
internal combustion engine which method comprises incorporating
into the fuel composition in one or more steps: a. a
hydrocarbyl-substituted aromatic compound; and b. a polyalkylene
amine to produce a fuel composition which comprises said additives
in combination and which on combustion in said engine produces less
particulate emissions than the particulate emissions produced when
combusting in said engine the fuel composition without said
combination of additives.
33. The method of claim 34, wherein the hydrocarbyl-substituted
aromatic compound is a Mannich Base additive and the polyalkylene
amine is a polyisobutylene amine.
34. The method of claim 34, wherein the hydrocarbyl-substituted
aromatic compound is present in the fuel composition at a
concentration of actives of from about 20 ppm to about 300 ppm, and
the polyalkylene amine is present in the fuel composition at a
concentration of actives of from about 50 ppm to about 500 ppm.
35. The method of claim 34, wherein the hydrocarbyl substituent of
the aromatic compound exhibits a number average molecular weight of
from about 700 to about 1500, and wherein the polyalkylene amine
contains a polyalkylene group that exhibits a number average
molecular weight of from about 700 to about 1500.
36. A method for controlling wear on at least one of the turbo, the
timing chain, the crank train, and the camshaft and valve train
assembly, and associated bearings and sealing systems, and/or for
maintaining the performance of the lubricant, and/or for
maintaining at least one of the exhaust gas recirculation system,
the exhaust gas after treatment system and the gasoline particulate
filters, and/or for limiting at least one of the octane requirement
increase and the propensity for pre-ignition in the engine, and/or
for preventing increases in turbo lag and response times, and or
for controlling the generation of complex poly-aromatic nuclei
(CPAN) in a direct-injection spark-ignition internal combustion
engine or a compression-ignition gasoline internal combustion
engine, which method comprises supplying to the engine a fuel
composition which comprises a combination of: a. a
hydrocarbyl-substituted aromatic compound; and b. a polyalkylene
amine.
37. The method of claim 36, wherein the method is for controlling
the generation of complex poly-aromatic nuclei (CPAN) in a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine, and
wherein the hydrocarbyl-substituted aromatic compound and the
polyalkylene amine being present in the fuel composition in an
amount such that substantially less complex poly-aromatic nuclei
(CPAN) are generated when the fuel composition is combusted in the
engine than when the same fuel composition without the combination
of the hydrocarbyl-substituted aromatic compound and the
polyalkylene amine is combusted in the engine.
Description
[0001] This invention relates to methods and uses and in particular
aspects to a method of controlling particulate emissions from a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine, and in
other aspects to the use of a combination of additives as a
particulate emissions controlling additive in a fuel composition
for a direct-injection spark-ignition internal combustion engine or
a compression-ignition gasoline internal combustion engine. The
invention also relates to methods for controlling the generation of
complex poly-aromatic nuclei (CPAN) in a direct-injection
spark-ignition internal combustion engine or a compression-ignition
gasoline internal combustion engine, and in other aspects to the
use of a combination of additives as a CPAN controlling additive in
a fuel composition for a direct-injection spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion 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] Vehicle emissions include particulate pollutants (PM), as
well as ozone precursors such as nitrogen oxides (NO.sub.x) and
hydrocarbons.
[0006] CPAN are thought to be precursors in the generation of
particulate emissions. Particulate emissions from gasoline direct
injection engines are 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.
[0007] Particulate emissions can impact the performance of an
engine. For instance, within the gas flow of an engine, they can
lead to clogging of the exhaust gas recirculation system, the
exhaust gas after treatment system and the gasoline particulate
filters. Particulate emissions can also lead to increases in turbo
lag and response times in the engine.
[0008] CPAN can also impact the performance of an engine in other
ways. For instance, it is known in the art that CPAN can form
soot-like particles that interfere with the anti-wear additive
function in the lubricant pathway. Accordingly, CPAN can lead to
wear on components in the lubricant pathway, such as the turbo, the
timing chain, the crank train, and the camshaft and valve train
assembly, including associated bearings and sealing systems.
Control of CPAN generation and subsequent ingress into the
lubricant will also maintain the performance of the lubricant
including the lubricant additive chemistries thereby extending the
required lubricant drain interval, especially under severe engine
operating conditions. Other CPAN derived materials are believed to
congregate within the combustion chamber. This can lead to an
increase in octane requirement, as well as greater propensity for
pre-ignition in the engine.
[0009] According to its abstract, US2004/118036 discloses that a
fuel composition containing an alkylene oxide-adducted hydrocarbyl
amide having from about 3 to 50 moles of alkylene oxide per mole of
hydrocarbyl amide may reduce the particulate emissions in an
internal combustion engine.
[0010] However, there remains a need for a fuel composition
comprising components which provides suitable detergency to a
direct-injection spark-ignition internal combustion engine, yet
controls particulate emissions, such as the number of particles
emitted from an engine.
[0011] According to its paragraph [0002], US2006/0277820 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.
[0012] Paragraph [0015] of US 2006/0277820 states: [0013] "Mannich
bases have been used in isolation or in combination with diamine to
reduce deposits on carburet[t] or 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."
[0014] Paragraph [0069] of US2006/0277820 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. Control of particulate emissions is not addressed by the
disclosure in US2006/0277820.
[0015] Therefore, there remains a need for methods and uses aspects
of which reduce or at least mitigate problems, for example as
identified above.
[0016] According to a first aspect of the present invention there
is provided a method of controlling particulate emissions from a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine which
method comprises supplying to the engine a fuel composition which
comprises a combination of:
[0017] a. a hydrocarbyl-substituted aromatic compound; and
[0018] b. a polyalkylene amine.
[0019] According to a further aspect of the present invention there
is provided the use as a particulate emissions controlling additive
in a fuel composition for a direct-injection spark-ignition
internal combustion engine or a compression-ignition gasoline
internal combustion engine of:
[0020] a. a hydrocarbyl-substituted aromatic compound; and
[0021] b. a polyalkylene amine.
[0022] According to a further aspect of the present invention there
is provided a method of reducing the particulate emitting tendency
of a fuel composition for use in a direct-injection spark-ignition
internal combustion engine or a compression-ignition gasoline
internal combustion engine which method comprises incorporating
into the fuel composition in one or more steps:
[0023] a. a hydrocarbyl-substituted aromatic compound; and
[0024] b. a polyalkylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in said engine produces less
particulate emissions than the particulate emissions produced when
using in said engine the fuel composition without said combination
of additives.
[0025] According to another aspect of the present invention there
is provided the use of an additive composition comprising a
combination of:
[0026] a. a hydrocarbyl-substituted aromatic compound; and
[0027] b. a polyalkylene amine
for improving the particulate emissions control performance of a
fuel composition in a direct-injection spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine.
[0028] According to another aspect of the present invention there
is provided a method of controlling the generation of complex
poly-aromatic nuclei (CPAN) in a direct-injection spark-ignition
internal combustion engine or a compression-ignition gasoline
internal combustion engine which method comprises supplying to the
engine a fuel composition which comprises a combination of:
[0029] a. a hydrocarbyl-substituted aromatic compound; and
[0030] b. a polyalkylene amine.
[0031] According to another aspect of the present invention there
is provided the use as a CPAN generation controlling additive in a
fuel composition for a direct-injection spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine of:
[0032] a. a hydrocarbyl-substituted aromatic compound; and
[0033] b. a polyalkylene amine.
[0034] According to another aspect of the present invention there
is provided a method of controlling wear on at least one of the
turbo, the timing chain, the crank train, and the camshaft and
valve train assembly, and associated bearings and sealing systems,
and/or for maintaining the performance of the lubricant, and/or for
maintaining at least one of the exhaust gas recirculation system,
the exhaust gas after treatment system and the gasoline particulate
filters, and/or for limiting at least one of the octane requirement
increase and the propensity for pre-ignition in the engine, and/or
for preventing increases in turbo lag and response times in a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine which
method comprises supplying to the engine a fuel composition which
comprises a combination of:
[0035] a. a hydrocarbyl-substituted aromatic compound; and
[0036] b. a polyalkylene amine.
[0037] According to a further aspect of the present invention there
is provided the use as an additive for controlling wear on at least
one of the turbo, the timing chain, the crank train, and the
camshaft and valve train assembly, and associated bearings and
sealing systems, and/or for maintaining the performance of the
lubricant, and/or for maintaining at least one of the exhaust gas
recirculation system, the exhaust gas after treatment system and
the gasoline particulate filters, and/or for limiting at least one
of the octane requirement increase and the propensity for
pre-ignition in the engine, and/or for preventing increases in
turbo lag and response times in a fuel composition for a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine of:
[0038] a. a hydrocarbyl-substituted aromatic compound; and
[0039] b. a polyalkylene amine.
[0040] In embodiments, the hydrocarbyl-substituted aromatic
compound is a Mannich base additive. In embodiments, the
polyalkylene amine is a polyisobutylene amine.
[0041] 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.
[0042] In particular it has been found that a fuel composition
comprising a combination of a hydrocarbyl-substituted aromatic
compound and a polyalkylene amine exhibits beneficial particulate
emissions control, such as control of the number of particles
emitted, when used in a direct-injection spark-ignition internal
combustion engine or a compression-ignition gasoline internal
combustion engine. A fuel composition comprising a combination of a
hydrocarbyl-substituted aromatic compound and a polyalkylene amine
may also exhibit beneficial CPAN generation control when used in a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine.
Polyalkylene Amine.
[0043] 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.
[0044] 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.
[0045] 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.
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
R.sub.2 and R.sub.3 are identical or different and are each
independently: [0046] hydrogen; [0047] an aliphatic or aromatic
hydrocarbyl group; [0048] a primary or secondary, aromatic or
aliphatic aminoalkylene group or polyaminoalkylene group; [0049] a
polyoxyalkylene group; [0050] a heteroaryl or heterocyclyl group;
or [0051] together with the nitrogen atom to which they are bonded
form a ring in which further hetero atoms may be present.
[0052] In at least some examples, R.sub.2 and R.sub.3 are identical
or different and are each independently:
hydrogen; alkyl; aryl; hydroxyalkyl; or an aminoalkylene group
represented by the general formula (II):
##STR00002## [0053] 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
a polyaminoalkylene group represented by the general formula
(III):
[0053] [--R.sub.4--NR.sub.5].sub.mR.sub.6 (III) [0054] 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 a polyoxyalkylene
group represented by the general formula (IV):
[0054] [--R.sub.4--O].sub.nX (IV) [0055] 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.
[0056] 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.
[0057] 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.
[0058] 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--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.
[0059] 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##
[0060] 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: [0061] Alk is a straight-chain or branched alkylene [0062]
m is an integer from 0 to 10; and [0063] 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 [0064]
alkylaryl group; a heteroaryl group or, together with the nitrogen
atom to which they are bonded, form a heterocyclic structure,
or
[0065] R.sub.11 and R.sub.12, together with the nitrogen atom to
which they are bonded, form a heterocyclic structure.
[0066] 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.
[0067] 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##
[0068] Highly reactive polyisobutenes may be made by methods
described for example in U.S. Pat. No. 4,152,499.
[0069] 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.
[0070] 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: [0071] (i) being derivable
or derived from isobutene and up to 20% by weight of n-butene;
[0072] (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; [0073] (iii) containing
at least 85% by weight isobutylene units; [0074] (iv) a
polydispersity in the range of from 1.05 to 7
[0075] 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.
[0076] 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.
[0077] In at least some examples the polyalkylene amine is
present/used in the fuel composition at a concentration of actives
of at least about 50 ppm, for example at a concentration of actives
of at least about 70 ppm. In at least some examples the
polyalkylene amine is present/used in the fuel composition at a
concentration as actives of up to about 500 ppm, for example at a
concentration of up to about 300 ppm. In at least some examples the
polyalkylene amine is present/used in the fuel composition at a
concentration of actives in the range of from about 50 ppm to about
500 ppm, such as from about 70 ppm to about 300 ppm. Concentration
of actives means the concentration of the active polyalkylene amine
disregarding for example, any solvent and the like. As will be
clear to the skilled person, the concentration of actives expressed
herein in terms of ppm is ppm by weight.
[0078] Typically, the polyalkylene amine will be present/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 500 ppm.
[0079] Where more than one polyalkylene amine is used, the total
concentration of the polyalkylene amines is as described
herein.
Hydrocarbyl-Substituted Aromatic Compound.
[0080] 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.
[0081] 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.
[0082] In embodiments, a Mannich Base additive may be used in the
fuel composition.
[0083] 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: [0084] at a temperature in the range of from 40.degree.
C. to 200.degree. C.; [0085] in the absence or presence of solvent;
[0086] for a reaction time in the range of from 2 to 4 hours; and
[0087] with azeotropic distillative removal of water
by-product.
[0088] Examples of aldehydes suitable for the preparation of
Mannich Base additives include: [0089] aliphatic aldehydes,
including for example, formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caprioaldehyde, heptaldehyde and
stearaldehyde; [0090] aromatic aldehydes including for example,
benzaldehyde and salicylaldehyde; and heterocyclic aldehydes
including for example, furfural aldehyde and thiophene
aldehyde.
[0091] Also useful in at least some examples are formaldehyde
precursors including for example paraformaldehyde and aqueous
formaldehyde solutions including for example formalin.
[0092] 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.
[0093] 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.
[0094] 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.
[0095] In at least some examples the hydrocarbyl substituents
contain some residual unsaturation but in general they are
substantially saturated.
[0096] 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).
[0097] 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.
[0098] 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 US20090071065.
[0099] 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.
[0100] 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.
[0101] 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.
[0102] 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: [0103] operating at a temperature in the
range of from room temperature to 95.degree. C.; [0104] reacting
the compounds alone or in the presence of an easily removable
solvent for example benzene, xylene, toluene, or solvent refined
neutral oil; [0105] using formaldehyde (e.g. formalin) as the
aldehyde; [0106] 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 [0107]
filtering the reaction product and diluting with solvent.
[0108] 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 alkyl 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.
[0109] 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.
[0110] 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.
[0111] Examples of representative di-substituted hydroxyaromatic
compounds include those represented by the general formula
(VII):
##STR00006##
[0112] 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.
[0113] 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.
[0114] Examples of suitable di-substituted hydroxyaromatic
compounds include those obtained or obtainable by alkylating
o-cresol with the high molecular weight polymers described
above.
[0115] 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.
[0116] Examples of representative secondary amines (ii) include
those represented by the general formula (VIII):
##STR00007##
[0117] 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.
[0118] 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##
[0119] 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, propyl, isopropyl and the like;
##STR00011##
[0120] 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 chromatography, with the proviso that at least one R is
H and one R is a hydrocarbyl substituent as hereinbefore
defined.
[0121] 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.
[0122] 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. In at least some
examples the hydrocarbyl-substituted hydroxyaromatic reactant is
obtained or obtainable from highly reactive polyisobutene.
[0123] 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.
[0124] Examples of suitable Mannich Base additives also include
those disclosed in, and/or obtained or obtainable by methods
described in US20090071065. 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##
[0125] 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. In at least
some examples polyolefin polymer hydrocarbyl substituents contain
at least 20%, for example 50%, or 70% of their olefin double bonds
at a terminal position on the carbon chain as the highly reactive
vinylidene isomer. 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.
[0126] 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.
[0127] In at least some examples the hydrocarbyl-substituted
aromatic compound is present/used in the fuel composition at a
concentration of actives of at least about 20 ppm, for example at a
concentration of actives of at least about 30 ppm. In at least some
examples, the hydrocarbyl-substituted aromatic compound is
present/used in the fuel composition at a concentration of actives
of up to about 300 ppm, for example at a concentration of up to
about 120 ppm. In at least some examples, the
hydrocarbyl-substituted aromatic compound is present/used in the
fuel composition at a concentration of actives in the range of from
about 20 ppm to about 300 ppm, such as from about 30 ppm to about
120 ppm. Concentration of actives means the concentration of the
active hydrocarbyl-substituted aromatic compound disregarding, for
example, any solvent and the like.
[0128] 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 300 ppm.
[0129] Where more than one hydrocarbyl-substituted aromatic
compound is present/used, the total concentration of the
hydrocarbyl-substituted aromatic compounds is as described
herein.
[0130] In some examples, the polyalkylene amine is present/used in
the fuel composition at a concentration of actives of from about 50
ppm to about 500 ppm and the hydrocarbyl-substituted aromatic
compound is present/used in the fuel composition at a concentration
of actives of from about 20 ppm to about 300 ppm. Typically, the
polyalkylene amine may be present/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 500 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 300 ppm.
[0131] 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. 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.
[0132] 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.
[0133] In at least some examples, a carrier fluid (sometimes also
called induction aid or fluidiser) is present/used in the fuel
composition, the uses and/or the methods. In at least some examples
more than one carrier fluid is present/used.
[0134] 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.
[0135] Examples of suitable carrier fluids are described for
example in US2009/0071065 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.
[0136] 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).
[0137] 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.
[0138] 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.
[0139] 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.
[0140] 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.).
[0141] 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.
[0142] Examples of poly(oxyalkylene) compounds include those
disclosed in, and/or obtained or obtainable by methods described
in, US248664, U.S. Pat. No. 2,425,845, U.S. Pat. No. 2,425,755 and
U.S. Pat. No. 2,457,139.
[0143] 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.
[0144] 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.
[0145] Examples of polyalkylene carrier fluids also include
hydrotreated polypropylenes, hydrotreated polybutenes, hydrotreated
polyisobutenes and the like.
[0146] 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.
[0147] In at least some examples the carrier fluid is present/used
in the fuel composition at a concentration of at least about 10
ppm, for example at a concentration of at least about 35 ppm. In at
least some examples, the carrier fluid is present/used in the fuel
composition at a concentration of up to about 500 ppm, for example
at a concentration of up to about 200 ppm. In at least some
examples, the carrier fluid is present/used in the fuel composition
at a concentration in the range of from about 10 ppm to about 500
ppm, such as from about 35 ppm to about 200 ppm.
[0148] Where more than one carrier fluid is present/used, the total
concentration of the carrier fluid is as described herein.
Fuel Composition
[0149] The fuel composition is suitable for use for example, in a
spark ignition internal combustion engine or a compression-ignition
gasoline internal combustion engine.
[0150] 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.
[0151] Examples of suitable fuel compositions include leaded and
unleaded fuel compositions.
[0152] 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.
[0153] 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/1, 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.
[0154] Examples of suitable fuel compositions include for example
hydrocarbon fuels, oxygenate fuels and combinations thereof.
[0155] 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.
[0156] 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 or compression-ignition gasoline 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.
[0157] According to an aspect of the present invention there is
provided a method of reducing the particulate emitting tendency
and/or CPAN emitting tendency of a fuel composition for use in a
direct-injection spark-ignition internal combustion engine or a
compression-ignition gasoline internal combustion engine which
method comprises incorporating into the fuel composition in one or
more steps:
[0158] a. a hydrocarbyl-substituted aromatic compound; and
[0159] b. a polyalkylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in said engine produces less
particulate emissions and/or CPAN than the particulate emissions
and/or CPAN produced when combusting in said engine the fuel
composition without said combination of additives.
[0160] 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.
[0161] In at least some examples the fuel composition and/or
additive concentrates, and/or additive packages and/or additive
part packs comprise at least one other fuel additive. In at least
some examples the method of reducing the particulate emitting
tendency and/or CPAN generating tendency of a fuel composition
comprises incorporating in one or more steps at least one other
fuel additive.
[0162] 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.
[0163] 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.
[0164] Examples of such other fuel additives 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.
[0165] Representative suitable and more suitable independent
amounts of additives (if present) in the fuel composition are given
in Table 1. The concentrations expressed in Table 1 are by weight
of active additive compounds that is, independent of any solvent or
diluent.
[0166] 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.
TABLE-US-00001 TABLE 1 Fuel Composition Suitable amount More
suitable amount (actives), (actives), if present ADDITIVE TYPE (by
weight) (by weight) Hydrocarbyl-substituted 20-300 ppm 30-120 ppm
aromatic compounds Polyalkylene amines 50-500 ppm 70-300 ppm
Carrier fluid 10-500 ppm 35-200 ppm Friction modifiers/ 10-200 ppm
anti-wear additives Corrosion inhibitors 1-20 ppm Octane improvers
and/or 5-30000 ppm combustion improvers Anti-oxidants 0.1-20 ppm
Dehazers/demulsifiers 0.1-20 ppm Dyes and/or markers 0.1-20 ppm
Odorants 1-20 ppm Anti-microbial agents 1-20 ppm Lubricity
improvers 10-200 ppm Valve seat recession additives 1-15000 ppm
[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] 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).
[0172] Examples of suitable valve seat recession additives include
inorganic salts of potassium or phosphorus.
[0173] 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.
[0174] 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.
[0175] 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 or as a marketing additive.
[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
marketing additive, for example at a terminal or distribution
point.
[0177] 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 2.0 L
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.
[0178] Particulate emissions may be measured by assessing the
number of particles emitted from an engine. The particles may have
a size in the range of from 23 nm to 2.5 .mu.m. 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).
[0179] Particulate emissions may be measured from a turbocharged
boosted direct injection spark-ignition internal combustion engine
(2.0 litre or less). The number of particles that are emitted from
the engine may be assessed once the engine has run for more than 12
hours, such as for more than 15 hours. The engine may be run at a
single load point. The load point may be representative of
real-world engine operation, such as motorway driving operation
(for example, at a speed of from about 80 km/h to 160 km/h).
[0180] The fuel compositions used in the present invention control
particulate emissions, such as the number of particles emitted, 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. 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 industry standard test method: CEC-F-20-A-98,
also known as the M111 test.
[0181] 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.
[0182] The invention will now be described by way of example only
with reference to the following drawings, experiments and example
in which the example according to the present invention is labelled
as Example 1 and Experiments not according to the present invention
are labelled alphabetically as Experiment A, Experiment B etc.
[0183] In the drawing FIG. 1 represents, in graph form, the
particulate emissions control performance for the fuel compositions
tested.
[0184] Intake valve deposit keep-clean performance were assessed
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.
[0185] 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 used in the
tests meets the legislative requirements of the European
Commission's Particle Measurement Programme (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 E10 gasoline base fuel for
use in the engine tests.
Experiment A--Mannich Base Only
[0186] The particulate emissions control performance of a fuel
containing Mannich Base additive was assessed. The amount of
Mannich Base additive used in the experiment was selected to give a
typical port fuel injection valve keep-clean performance.
Experiment B--Combination of Mannich Base Additive and Mannich Base
Additive
[0187] The particulate emissions control performance of a fuel
containing a combination of two Mannich Base additives was
assessed. The combined amount of Mannich Base additives used in the
experiment was selected to give a typical port fuel injection valve
keep-clean performance and which was comparable to that of the fuel
composition used in Experiment A.
Experiment C--Polyisobutylene Amine Only
[0188] The particulate emissions control performance of a fuel
containing PIBA additive was assessed. The amount of PIBA additive
used in the experiment was selected to give a typical port fuel
injection valve keep-clean performance and which was comparable to
that of the fuel composition used in Experiments A and B.
Example 1--Combination of Mannich Base Additive and Polyisobutylene
Amine
[0189] The particulate emissions control performance of a fuel
containing a combination of Mannich Base additive and PIBA additive
was assessed. The combined amount of Mannich Base and PIBA
additives used in the experiment was selected to give a typical
port fuel injection valve keep-clean performance and which was
comparable to that of the fuel composition used in Experiments A, B
and C.
[0190] Tests to determine the increase in injector pulse width over
the 15 hour test cycle were also carried out, and demonstrate that
fuel compositions containing 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.
[0191] The particulate emissions control performance of the
different fuel compositions is shown graph form in FIG. 1, with a
reference base fuel as comparison.
[0192] The data shown in FIG. 1 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. In particular, the data show that the fuel composition
comprising a Mannich Base additive in combination with a
polyisobutylene amine exhibits greater particulate emissions
control in a direct-injection spark-ignition internal combustion
engine than an un-additised fuel, a fuel containing only
polyisobutylene amine or only a Mannich Base additive, and a fuel
containing a combination of Mannich Base additives. The comparison
of the fuels is made at concentrations of additives providing
comparable keep-clean performance, when measured using the industry
standard test method: CEC-F-20-A-98.
[0193] It can be inferred from the data that the generation of CPAN
is controlled by a fuel composition comprising a Mannich Base
additive and a polyisobutylene amine.
[0194] These data illustrate a method of controlling particulate
emissions from a direct-injection spark-ignition internal
combustion engine which method comprises supplying to the engine a
fuel composition which comprises a combination of:
[0195] a. a hydrocarbyl-substituted aromatic compound; and
[0196] b. a polyalkylene amine.
[0197] The data also illustrate the use as a particulate emissions
controlling additive in a fuel composition for a direct-injection
spark-ignition internal combustion engine of:
[0198] a. a hydrocarbyl-substituted aromatic compound; and
[0199] b. a polyalkylene amine.
[0200] The data also illustrate a method of reducing the
particulate emitting tendency of a fuel composition for use in a
direct-injection spark-ignition internal combustion engine which
method comprises incorporating into the fuel composition in one or
more steps:
[0201] a. a hydrocarbyl-substituted aromatic compound; and
[0202] b. a polyalkylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a direct-injection
spark-ignition internal combustion engine produces less particulate
emissions than the particulate emissions produced when combusting
in said engine the fuel composition without said combination of
additives.
[0203] The data also illustrate that the particulate emissions
control performance of a fuel composition comprising a combination
of a hydrocarbyl-substituted aromatic compound and a polyalkylene
amine is improved relative to that of a fuel composition which
comprises a polyalkylene amine but does not comprise a
hydrocarbyl-substituted aromatic compound, and relative to that of
a fuel composition which comprises a hydrocarbyl-substituted
aromatic compound but does not comprise a polyalkylene amine.
Accordingly, in some examples, an additive composition comprising a
combination of:
[0204] a. a hydrocarbyl-substituted aromatic compound; and
[0205] b. a polyalkylene amine
is used for improving the particulate emissions control performance
of a fuel composition in a direct-injection spark-ignition internal
combustion engine.
* * * * *