U.S. patent application number 14/905052 was filed with the patent office on 2016-06-16 for methods and uses for intake-valve and direct-injector deposit clean-up.
This patent application is currently assigned to BP OIL INTERNATIONAL LIMITED. The applicant listed for this patent is Robert Edward ALLAN, BP OIL INTERNATIONAL LIMITED, Ross Alexander DEWHURST, Michael John GRUNDY, David Michael WILLIAMSON. Invention is credited to Robert Edward ALLAN, Ross Alexander DEWHURST, Michael John GRUNDY, David Michael WILLIAMSON.
Application Number | 20160168498 14/905052 |
Document ID | / |
Family ID | 49029036 |
Filed Date | 2016-06-16 |
United States Patent
Application |
20160168498 |
Kind Code |
A1 |
ALLAN; Robert Edward ; et
al. |
June 16, 2016 |
Methods and Uses for Intake-Valve and Direct-Injector Deposit
Clean-Up
Abstract
The use as an intake valve deposit clean-up additive in a fuel
composition for a port fuel injection spark-ignition internal
combustion engine or a fuel injector deposit clean-up additive in a
fuel composition for a direct injection spark-ignition internal
combustion engine of a combination of: a. at least one
hydrocarbyl-substituted aromatic compound; and b. at least one
polyalkylene amine.
Inventors: |
ALLAN; Robert Edward;
(Berkshire, GB) ; DEWHURST; Ross Alexander;
(Berkshire, GB) ; GRUNDY; Michael John;
(Berkshire, GB) ; WILLIAMSON; David Michael;
(Berkshire, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ALLAN; Robert Edward
DEWHURST; Ross Alexander
GRUNDY; Michael John
WILLIAMSON; David Michael
BP OIL INTERNATIONAL LIMITED |
Berkshire
Berkshire
Berkshire
Berkshire
Middlesex |
|
GB
GB
GB
GB
GB |
|
|
Assignee: |
BP OIL INTERNATIONAL
LIMITED
Middlesex
GB
|
Family ID: |
49029036 |
Appl. No.: |
14/905052 |
Filed: |
August 21, 2014 |
PCT Filed: |
August 21, 2014 |
PCT NO: |
PCT/EP2014/067869 |
371 Date: |
January 14, 2016 |
Current U.S.
Class: |
44/424 |
Current CPC
Class: |
C10L 1/198 20130101;
C10L 1/1683 20130101; C10L 1/221 20130101; C10L 2300/20 20130101;
C10L 1/238 20130101; C10L 1/22 20130101; C10L 2200/0259 20130101;
C10L 10/18 20130101; C10L 10/06 20130101; C10L 2270/023 20130101;
C10L 1/2383 20130101; C10L 1/1691 20130101; C10L 1/2225 20130101;
C10L 1/143 20130101; C10L 1/2222 20130101; C10L 1/2387 20130101;
C10L 2200/0423 20130101 |
International
Class: |
C10L 10/06 20060101
C10L010/06; C10L 1/222 20060101 C10L001/222 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 27, 2013 |
EP |
13181878.3 |
Claims
1-11. (canceled)
12. A method of improving the port fuel injection intake valve
deposit clean-up performance or the direct injection fuel injector
deposit clean-up performance of a fuel composition for use in a
spark-ignition internal combustion engine which method comprises
incorporating into the fuel composition in one or more steps: a. at
least one hydrocarbyl-substituted aromatic compound, such as a
Mannich Base detergent; and b. at least one polyalkylene amine,
such as a polyisobutylene amine to produce a fuel composition which
comprises said additives in combination and which on combustion in
a spark-ignition engine produces greater port fuel injection intake
valve or direct injection fuel injector deposit clean-up
performance than the clean-up performance when combusting in said
engine the fuel composition without said combination of
additives.
13. The method of claim 12, wherein the at least one
hydrocarbyl-substituted aromatic compound is present in the fuel
composition at a concentration of actives of from 20 ppm to 200
ppm.
14. The method of claim 12, wherein the hydrocarbyl substituent of
the aromatic compound exhibits a number average molecular weight of
from 700 to 1500.
15. The method of claim 12, wherein the hydrocarbyl substituent of
the aromatic compound is or comprises polyisobutylene.
16. The method of claim 12, wherein the at least one polylalkylene
amine is present in the fuel composition at a concentration of
actives of from 50 ppm to 500 ppm.
17. The method of claim 12, wherein the polyalkylene amine contains
a polyalkylene group that exhibits a number average molecular
weight of from 700 to 1500.
18. The method of claim 12, wherein the weight ratio of actives of
polyalkylene amine:hydrocarbyl-substituted aromatic compound in the
fuel composition is in the range of from 5:1 to 1:5.
19. The method of claim 12, wherein the fuel is for a port fuel
injection engine.
20. A method of removing deposits from the intake valves in a port
fuel injection spark-ignition internal combustion engine or the
fuel injectors in a direct injection spark-ignition internal
combustion engine which method comprises supplying to the engine
through the port fuel injection intake valves or through the direct
injection fuel injectors, a fuel composition which comprises a
combination of: a. at least one hydrocarbyl-substituted aromatic
compound, such as a Mannich Base detergent; and b. at least one
polyalkylene amine, such as a polyisobutylene amine.
21. The method of claim 20, wherein the at least one
hydrocarbyl-substituted aromatic compound is present in the fuel
composition at a concentration of actives of from 20 ppm to 200
ppm.
22. The method of claim 20, wherein the hydrocarbyl substituent of
the aromatic compound exhibits a number average molecular weight of
from 700 to 1500.
23. The method of claim 20, wherein the hydrocarbyl substituent of
the aromatic compound is or comprises polyisobutylene.
24. The method of claim 20, wherein the at least one polylalkylene
amine is present in the fuel composition at a concentration of
actives of from 50 ppm to 500 ppm.
25. The method of claim 20, wherein the polyalkylene amine contains
a polyalkylene group that exhibits a number average molecular
weight of from 700 to 1500.
26. The method of claim 20, wherein the weight ratio of actives of
polyalkylene amine:hydrocarbyl-substituted aromatic compound in the
fuel composition is in the range of from 5:1 to 1:5.
27. The method of claim 20, wherein the fuel is for a port fuel
injection engine.
Description
[0001] This invention relates to methods and uses and in particular
aspects to a method of improving the port fuel injection intake
valve or direct injection fuel injector deposit clean-up
performance of a fuel composition for use in a spark-ignition
internal combustion engine, and in other aspects to the use of a
combination of additives as a port fuel injection intake valve or
direct injection fuel injector deposit clean-up additive in a fuel
composition for a spark-ignition 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); and [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 or a direct
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] According to its abstract, U.S. Pat. No. 4,166,726 relates
to a fuel additive comprising a mixture of a polyalkylene amine and
the reaction product of an alkylphenol, an aldehyde and an amine,
which is said to provide stability in preventing thermal
degradation of fuels, particularly fuels for compression ignition
engines.
[0007] According to its abstract, US2005/0215441 relates to a
method of operating an internal combustion engine in which a
nitrogen-containing detergent composition is introduced into a
combustion chamber of the engine wherein the detergent composition
contains (A) a reaction product of a hydrocarbyl-substituted
acylating agent and an amine, (B) a hydrocarbyl-substituted amine,
(C) a Mannich reaction product, (D) a high molecular weight
polyetheramine, or (E) a mixture thereof.
[0008] In paragraph [0077] to [paragraph [0081] of US2005/0215441
experiments are described using Ford pre-production 3-cylinder
direct injection spark ignited 1.125 L engines equipped with EGR.
The additised fuel contained a Mannich reaction product. The effect
of addition to the fuel of dispersant/detergent on the distance
accumulated prior to TBN:TAN cross-over of the lubricant was
reported.
[0009] According to its paragraph [0030], US 2008/0086936 relates
to a method of reducing deposits formed in an internal combustion
engine combusting an ethanol-gasoline blend, said method comprising
combining the blend with at least one additive selected from the
group consisting of 2,6-di t-butyl phenol antioxidant,
methylcyclopentadienyl manganese tricarbonyl combustion improver
and octane enhancer, oleic acid plus N,N' dimethylcyclohexylarnine,
dodecenyl succinic acid, polyisobutylene amine dispersant, 1,2
propane diamine salicylaldehyde metal deactivator, cresol Mannich
Base dispersant, diethanol amide of isostearic acid friction
modifier, and 2-ethyl hexyl nitrate combustion improver, whereby
the deposits formed in said engine are less than the deposits
formed in the engine when combusting the blend without the at least
one additive.
[0010] According to its abstract, US2003/0029077 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 fueling the
engine with the fuel composition which is said to result in control
of deposits in the fuel induction system.
[0011] According to its paragraph [0002], US2006/0277820 relates to
a deposit control additive composition 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 carburettor surfaces. As disclosed in the
present application 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 carbutet[t]or and keep port fuel injectors and fuel
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.
[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 improving the port fuel injection intake
valve deposit clean-up performance or the direct injection fuel
injector deposit clean-up performance of a fuel composition for use
in a spark-ignition internal combustion engine which method
comprises incorporating into the fuel composition in one or more
steps:
[0017] a. at least one hydrocarbyl-substituted aromatic compound;
and
[0018] b. at least one polyalkylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a spark-ignition engine
produces greater port fuel injection intake valve or direct
injection fuel injector deposit clean-up performance than the
clean-up performance when combusting in said engine the fuel
composition without said combination of additives.
[0019] In an embodiment, there is provided a method of improving
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 which method comprises
incorporating into the fuel composition in one or more steps:
[0020] a. at least one Mannich Base detergent; and
[0021] b. at least one polyisobutylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a port fuel injection
spark-ignition engine produces greater intake valve deposit
clean-up performance than the intake valve clean-up performance
when combusting in said engine the fuel composition without said
combination of additives.
[0022] According to a further aspect of the present invention there
is provided a method of removing deposits from the intake valves in
a port fuel injection spark-ignition internal combustion engine or
the fuel injectors in a direct injection spark-ignition internal
combustion engine which method comprises supplying to the engine
through the port fuel injection intake valves or through the direct
injection fuel injectors, a fuel composition which comprises a
combination of:
[0023] a. at least one hydrocarbyl-substituted aromatic compound;
and
[0024] b. at least one polyalkylene amine.
[0025] In an embodiment, there is provided a method of removing
deposits from the air intake valves in a port fuel injection
spark-ignition internal combustion engine which method comprises
supplying to the engine through the port fuel injection intake
valves, a fuel composition which comprises a combination of:
[0026] a. at least one Mannich Base detergent; and
[0027] b. at least one polyisobutylene amine.
[0028] According to a further aspect of the present invention,
there is provided the use as an intake valve deposit clean-up
additive in a fuel composition for a port fuel injection
spark-ignition internal combustion engine or a fuel injector
deposit clean-up additive in a fuel composition for a direct
injection spark-ignition internal combustion engine of a
combination of:
[0029] a. at least one hydrocarbyl-substituted aromatic compound;
and
[0030] b. at least one polyalkylene amine.
[0031] In an embodiment, there is provided the use as an intake
valve deposit clean-up additive in a fuel composition for a port
fuel injection spark-ignition internal combustion engine of a
combination of:
[0032] a. at least one Mannich Base detergent; and
[0033] b. at least one polyisobutylene amine.
[0034] According to another aspect of the present invention there
is provided the use of an additive composition comprising a
combination of:
[0035] a. at least one hydrocarbyl-substituted aromatic compound;
and
[0036] b. at least one polyalkylene amine
for improving the intake valve deposit clean-up performance
response of a fuel composition in a port fuel injection
spark-ignition internal combustion engine or the fuel injector
deposit clean-up performance response of a fuel composition in a
direct injection spark-ignition internal combustion engine as the
treat rate of the additive composition increases.
[0037] In an embodiment, there is provided the use of an additive
composition comprising a combination of:
[0038] a. at least one Mannich Base detergent; and
[0039] b. at least one polyisobutylene amine
for improving the intake valve deposit clean-up performance
response of a fuel composition in a port fuel injection
spark-ignition internal combustion engine as the treat rate of the
additive composition increases.
[0040] Aspects of the present invention address the technical
problems identified and others, by the use in combination of at
least one hydrocarbyl-substituted aromatic compound, such as a
Mannich Base detergent and at least one polyalkylene amine, such as
a polyisobutylene amine.
[0041] In particular it has been found that a fuel composition
comprising a combination of at least one hydrocarbyl-substituted
aromatic compound, such as a Mannich Base detergent, and at least
one polyalkylene amine, such as a 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 in at least some
examples, exhibits a beneficially steep gradient for performance
versus treat rate response, which in at least some examples, is
steeper than the gradient for conventional deposit control
additives. The fuel composition may also exhibit beneficial fuel
injector deposit clean-up performance when used in a direct
injection spark-ignition internal combustion engine.
[0042] It will be appreciated that when the fuel composition is
used for port fuel injection intake valve deposit clean-up, it will
be used in a port fuel injection engine. When the fuel composition
is used for direct injection fuel injector clean-up, it will be
used in a direct injection 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] Accordingly, in embodiments, at least one polyisobutylene
amine may be used in the fuel composition.
[0045] 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.
[0046] 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.
[0047] 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
[0048] R.sub.2 and R.sub.3 are identical or different and are each
independently: [0049] hydrogen; [0050] an aliphatic or aromatic
hydrocarbyl group; [0051] a primary or secondary, aromatic or
aliphatic aminoalkylene group or polyaminoalkylene group; [0052] a
polyoxyalkylene group; [0053] a heteroaryl or heterocyclyl group;
or [0054] together with the nitrogen atom to which they are bonded
form a ring in which further hetero atoms may be present.
[0055] In at least some examples, R.sub.2 and R.sub.3 are identical
or different and are each independently: [0056] hydrogen; [0057]
alkyl; [0058] aryl; [0059] hydroxyalkyl; or [0060] an aminoalkylene
group represented by the general formula (II):
[0060] ##STR00002## [0061] 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
[0062] a polyaminoalkylene group represented by the general formula
(III):
[0062] [--R.sub.4--NR.sub.5].sub.m R.sub.6 (III) [0063] 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 [0064] a
polyoxyalkylene group represented by the general formula (IV):
[0064] [--R.sub.4--O--].sub.nX (IV) [0065] 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.
[0066] 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.
[0067] 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.
[0068] 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, [0069]
--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, [0070]
--[--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.
[0071] 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##
[0072] 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 hetaryl group; an alkylene-imine group represented by the
formula (VI):
##STR00004##
wherein: [0073] Alk is a straight-chain or branched alkylene [0074]
m is an integer from 0 to 10; and [0075] 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 hetaryl group or, together with the nitrogen atom to which
they are bonded, form a heterocyclic structure, or [0076] R.sub.11
and R.sub.12, together with the nitrogen atom to which they are
bonded, form a heterocyclic structure.
[0077] 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.
[0078] 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##
[0079] Highly reactive polyisobutenes may be made by methods
described for example in U.S. Pat. No. 4,152,499.
[0080] In at least some examples the polyisobutylene amine contains
a polyisobutenic group that exhibits a number average molecular
weight of from 200 to 10000, for example from 500 to 5000 or from
700 to 1500 or from 800 to 1200 or from 850 to 1100, for example
about 1000.
[0081] 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: [0082] (i) being derivable
or derived from isobutene and up to 20% by weight of n-butene;
[0083] (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; [0084] (iii) containing
at least 85% by weight isobutylene units; [0085] (iv) a
polydispersity in the range of from 1.05 to 7
[0086] 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.
[0087] In at least some examples the polyalkylene amine, such as
the polyisobutylene amine is present/used in the fuel composition
at a concentration of actives of at least 50 ppm, for example at a
concentration of actives of at least 100 ppm. In at least some
examples the polyisobutylene amine is present/used in the fuel
composition at a concentration as actives of up to 500 ppm, for
example at a concentration of up to 300 ppm. In at least some
examples the polyalkylene amine, such as the polyisobutylene amine
is present/used in the fuel composition at a concentration of
actives in the range of from 50 ppm to 500 ppm, for example at a
concentration of actives in the range of from 50 ppm to 300 ppm,
such as from 100 ppm to 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.
[0088] Typically, the at least one polyalkylene amine, such as the
at least one polyisobutylene amine, will be present/used in the
fuel composition at a concentration of actives of from 50 ppm to
160 ppm. In some examples, however, higher treat rates may be used.
In such instances, the at least one polyalkylene amine may be
present/used in the fuel composition at a concentration of from 160
ppm to 500 ppm.
Hydrocarbyl-Substituted Aromatic Compound.
[0089] The at least one 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.
[0090] The hydrocarbyl substituent of the hydrocarbyl-substituted
aromatic compound may exhibit a number average molecular weight of
from 700 to 1500, such as from 900 to 1300.
[0091] In embodiments, at least one Mannich Base detergent may be
used in the fuel composition.
[0092] Examples of Mannich Base detergents include those obtained
or obtainable by the reaction of at least one
hydrocarbyl-substituted hydroxyaromatic compound, at least one
amine and at least one aldehyde under Mannich condensation reaction
conditions. Suitable reaction conditions include at least one (for
example, all) of the following conditions: [0093] at a temperature
in the range of from 40.degree. C. to 200.degree. C.; [0094] in the
absence or presence of solvent; [0095] for a reaction time in the
range of from 2 to 4 hours; and [0096] with azeotropic distillative
removal of water by-product.
[0097] Examples of aldehydes suitable for the preparation of
Mannich Base detergents include: [0098] aliphatic aldehydes,
including for example, formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caprioaldehyde, heptaldehyde and
stearaldehyde; [0099] aromatic aldehydes including for example,
benzaldehyde and salicylaldehyde; and heterocyclic aldehydes
including for example, furfural aldehyde and thiophene
aldehyde.
[0100] Also useful in at least some examples are formaldehyde
precursors including for example paraformaldehyde and aqueous
formaldehyde solutions including for example formalin.
[0101] 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.
[0102] Examples of suitable Mannich Base detergents include Mannich
Base detergents in which the hydrocarbyl substituent of the
aromatic group is or comprises polyisobutylene. Such compounds are
sometimes called PIB-Mannich Base detergents.
[0103] 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.
[0104] In at least some examples the hydrocarbyl substituents
contain some residual unsaturation but in general they are
substantially saturated.
[0105] 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).
[0106] In some examples, the hydrocarbyl substituent of the
hydroxyaromatic compound used to prepare the Mannich Base
detergent, which in some instances is or comprises polyisobutylene,
may exhibit a number average molecular weight of from 700 to 1500,
such as from 900 to 1300.
[0107] Examples of suitable Mannich Base detergents 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.
[0108] Examples of suitable Mannich Base detergents 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 detergents 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.
[0109] 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.
[0110] 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.
[0111] Examples of suitable Mannich Base detergents 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 detergents 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.
[0112] Suitable reaction conditions include one or more of the
following: [0113] operating at a temperature in the range of from
room temperature to 95.degree. C.; [0114] reacting the compounds
alone or in the presence of an easily removable solvent for example
benzene, xylene, toluene, or solvent refined neutral oil; [0115]
using formaldehyde (e.g. formalin) as the aldehyde; [0116] 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 [0117] filtering the reaction product
and diluting with solvent.
[0118] 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.
[0119] Examples of suitable Mannich Base detergents 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 detergents 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.
[0120] 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.
[0121] Examples of representative di-substituted hydroxyaromatic
compounds include those represented by the general formula
(VII):
##STR00006##
[0122] 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.
[0123] 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.
[0124] Examples of suitable di-substituted hydroxyaromatic
compounds include those obtained or obtainable by alkylating
o-cresol with the high molecular weight polymers described
above.
[0125] 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.
[0126] Examples of representative secondary amines (ii) include
those represented by the general formula (VIII):
##STR00007##
[0127] 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.
[0128] Examples of suitable Mannich Base detergents 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 detergents 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##
[0129] 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.
[0130] 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##
[0131] 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.
[0132] 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.
[0133] 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.
[0134] 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.
[0135] Examples of suitable Mannich Base detergents also include
those disclosed in, and/or obtained or obtainable by methods
described in US20090071065. Thus, examples of suitable Mannich Base
detergents 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##
[0136] 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.
[0137] In at least some examples the at least one
hydrocarbyl-substituted aromatic compound, such as the at least one
Mannich Base detergent, is present in the fuel composition at a
concentration of actives in the range of from 10 ppm to 500 ppm,
for example in the range of from 20 to 200 ppm, such as from 20 to
100 ppm. Concentration of actives means the concentration of the
active hydrocarbyl-substituted aromatic compound disregarding, for
example, any solvent and the like.
[0138] Typically, the at least one hydrocarbyl-substituted aromatic
compound, such as the at least one Mannich Base detergent, will be
present/used in the fuel composition at a concentration of actives
of from 20 ppm to 70 ppm. In some examples, however, higher treat
rates may be used. In such instances, the at least one
hydrocarbyl-substituted aromatic compound may be present/used in
the fuel composition at a concentration of from 70 ppm to 200
ppm.
[0139] In some examples, the at least one polyalkylene amine is
present/used in the fuel composition at a concentration of actives
of from 50 ppm to 500 ppm and the at least one
hydrocarbyl-substituted aromatic compound is present/used in the
fuel composition at a concentration of actives of from 20 ppm to
200 ppm. Typically, the at least one polyalkylene amine may be
present/used in the fuel composition at a concentration of actives
of from 50 ppm to 160 ppm and the at least one
hydrocarbyl-substituted aromatic compound may be present/used in
the fuel composition at a concentration of actives of from 20 ppm
to 70 ppm. However, in some examples, the at least one polyalkylene
amine may be present/used in the fuel composition at a
concentration of actives of from 160 ppm to 500 ppm and the
hydrocarbyl-substituted aromatic compound may be present/used in
the fuel composition at a concentration of actives of from 70 ppm
to 200 ppm. In at least some examples the weight ratio of actives
of the at least one polyalkylene amine:the at least one
hydrocarbyl-substituted aromatic compound is in the range of 10:1
to 1:10 for example 5:1 to 1:5. Where a polyisobutylene amine and
Mannich Base detergent are used, the weight ratio of actives of
polyisobutylene amine:Mannich Base detergent is in the range of
10:1 to 1:10 for example 5:1 to 1:5. Typically, the at least one
polyalkylene amine (such as polyisobutylene amine), contains a
polyalkylene group that exhibits a number average molecular weight
of from 700 to 1500 (e.g. from 800 to 1200) and the hydrocarbyl
substituent of the at least one hydrocarbyl-substituted aromatic
compound (such as a Mannich Base detergent), which in some
instances is or comprises polyisobutylene, exhibits a number
average molecular weight of from 700 to 1500 (e.g. 900 to
1300).
Carrier Fluid.
[0140] In at least some examples, at least one 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.
[0141] In at least some examples the at least one carrier fluid is
provided with the polyisobutylene amine. In at least some examples
the at least one carrier fluid is provided with the Mannich Base
detergent. In at least some examples at least one carrier fluid is
provided with each of the at least one polyisobutylene amine and
the at least one Mannich Base detergent, which carrier fluids may
be the same or different. In at least some examples the carrier
fluid is provided independently of the at least one polyisobutylene
amine and the at least one Mannich Base detergent.
[0142] 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.
[0143] 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).
[0144] 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.
[0145] 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.
[0146] 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.
[0147] 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.).
[0148] 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.
[0149] 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.
[0150] 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.
[0151] 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.
[0152] Examples of polyalkylene carrier fluids also include
hydrotreated polypropylenes, hydrotreated polybutenes, hydrotreated
polyisobutenes and the like.
[0153] 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
[0154] 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.
Fuel Composition
[0155] The fuel composition is suitable for use for example, in a
spark ignition internal combustion engine.
[0156] 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.
[0157] Examples of suitable fuel compositions include leaded and
unleaded fuel compositions.
[0158] In at least some examples the fuel composition meets the
requirements of EN 228, for example as set out in BS EN 228:2008.
In at least some examples the fuel composition meets the
requirements of ASTM D 4814-09b.
[0159] 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 228:2008:--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.
[0160] Examples of suitable fuel compositions include for example
hydrocarbon fuels, oxygenate fuels and combinations thereof.
[0161] 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.
[0162] 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.
[0163] According to an aspect of the present invention there is
provided a method of improving the port fuel injection intake valve
deposit clean-up performance or the direct injection fuel injector
clean-up performance of a fuel composition for use in a
spark-ignition internal combustion engine which method comprises
incorporating into the fuel composition in one or more steps:
[0164] a. at least one hydrocarbyl-substituted aromatic compound;
and
[0165] b. at least one polyalkylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a spark-ignition engine
produces greater port fuel injector intake valve deposit clean-up
performance or direction injection fuel injector clean-up
performance than the clean-up performance when combusting in said
engine the fuel composition without said combination of
additives.
[0166] In at least some examples, the at least one
hydrocarbyl-substituted aromatic compound and the at least one
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.
[0167] 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 improving the port fuel injection
intake valve deposit clean-up performance of a fuel composition
comprises incorporating in one or more steps at least one other
fuel additive.
[0168] 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.
[0169] 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.
[0170] Examples of such other fuel additives include friction
modifiers, antiwear additives, corrosion inhibitors,
dehazers/demulsifiers, dyes, markers, odorants, octane improvers,
combustion modifiers, antioxidants, antimicrobial agents, lubricity
improvers and valve seat recession additives.
[0171] 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.
[0172] 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 More amount
suitable amount (actives), (by (actives), if present ADDITIVE TYPE
weight) (by weight) at least one hydrocarbyl-substituted 10-500 ppm
20-100 ppm aromatic compound, such as a Mannich Base detergent at
least one polyalkylene amine, 50-500 ppm 50-300 ppm such as a
polyisobutylene amine e.g. 100-300 ppm Friction modifiers/ 10-200
ppm anti wear additives Corrosion inhibitors 1-20 ppm Octane
improvers and/ 5-10000 ppm or 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
[0173] 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).
[0174] Examples of suitable corrosion inhibitors include ammonium
salts of organic carboxylic acids, amines and heterocyclic
aromatics, for example alkylamines, imidazolines and
tolyltriazoles.
[0175] Examples of suitable non-metallic octane improvers include
N-methyl aniline.
[0176] 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.
[0177] 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).
[0178] Examples of suitable valve seat recession additives include
inorganic salts of potassium or phosphorus.
[0179] 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.
[0180] 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.
[0181] In at least some examples the at least one
hydrocarbyl-substituted aromatic compound and the at least one
polyalkylene amine are incorporated or admixed with other
components of the fuel composition as a refinery additive or as a
marketing additive.
[0182] In at least some examples the at least one
hydrocarbyl-substituted aromatic compound and the at least one
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.
[0183] 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 2.3 L Ranger engine and MB M111
engine
[0184] 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.
[0185] The fuel composition is preferably used in a port fuel
injection spark-ignition internal combustion engine to clean-up
deposits that may be found on a port fuel injection intake valve.
The fuel compositions may also be used in a direct injection
spark-ignition internal combustion engine to clean-up deposits that
may be found on a direct injection fuel injector.
[0186] 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 based upon the US industry standard test method: ASTM
D-6201 (version 04, 2009), this is sometimes also called the Ford
2.3 L "Ranger" engine test after the engine that is used.
[0187] 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. For example
the deposits on the port fuel injection intake valves may be
assessed according to ASTMD 6201 (version 04,2009).
[0188] Methods for measuring the direct injection fuel injector
clean-up performance of a fuel include the operation of a direct
injection engine with an unadditised fuel over a "dirty-up" cycle
in which the build-up of deposits is measured by changes in
parameters calculated by the electronic control unit (ECU) which
relate to the operation of the injectors. A further "clean-up"
cycle is then run using the additised fuel in which a reversal of
the changes observed during the dirty-up cycle is measured.
[0189] A further method for measuring the direct injection fuel
injector clean-up performance of a fuel includes the operation of a
dirty-up and clean-up cycle, as above, in which a measurement of
the flow rate of the injectors of the direct injection engine is
taken before the dirty-up, after the dirty-up but before the
clean-up, and after the clean-up. The changes in flow rate over the
dirty-up cycle and over the clean-up cycle are then calculated.
Subsequently the percentage of restoration of flow rate of the
clean-up compared to the dirty-up may be calculated.
[0190] Further aspects of the present invention include the
aspects, embodiments, instances and examples defined above but in
which a Mannich Base detergent is used as component a. In these
aspects, the Mannich Base detergent may be, but does not have to
be, a hydrocarbyl-substituted aromatic compound.
[0191] According to these further aspects, there is provided a
method of improving 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 which method
comprises incorporating into the fuel composition in one or more
steps:
[0192] a. at least one Mannich Base detergent; and
[0193] b. at least one polyisobutylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a port fuel injection
spark-ignition engine produces greater intake valve deposit
clean-up performance than the intake valve clean-up performance
when combusting in said engine the fuel composition without said
combination of additives.
[0194] According to these further aspects, there is also provided
the use as an intake valve deposit clean-up additive in a fuel
composition for a port fuel injection spark-ignition internal
combustion engine of a combination of:
[0195] a. at least one Mannich Base detergent; and
[0196] b. at least one polyisobutylene amine.
[0197] According to these further aspects, there is also provided a
method of removing deposits from the air intake valves in a port
fuel injection spark-ignition internal combustion engine which
method comprises supplying to the engine through the port fuel
injection intake valves, a fuel composition which comprises a
combination of:
[0198] a. at least one Mannich Base detergent; and
[0199] b. at least one polyisobutylene amine.
[0200] In these further aspects, the polyisobutylene amine may be
present/used in the fuel composition at a concentration of actives
of at least 50 ppm, for example at a concentration of actives of at
least 100 ppm. In at least some examples the polyisobutylene amine
is present/used in the fuel composition at a concentration as
actives of up to 500 ppm, for example at a concentration of up to
300 ppm. In at least some examples the polyisobutylene amine is
present/used in the fuel composition at a concentration of actives
in the range of from 50 ppm to 500 ppm, for example at a
concentration of actives in the range of from 100 ppm to 300
ppm.
[0201] In these further aspects, the Mannich Base detergent may be
present in the fuel composition at a concentration of actives in
the range of from 10 ppm to 500 ppm, for example in the range of
from 20 to 100 ppm. Concentration of actives means the
concentration of the active Mannich Base detergent disregarding for
example, any solvent and the like.
[0202] In these further aspects, the weight ratio of actives of
polyisobutylene amine: Mannich Base detergent may be in the range
of 10:1 to 1:10 for example 5:1 to 1:5.
[0203] In these further aspects, the polyisobutylene amine may
contains a polyisobutenic group that exhibits a number average
molecular weight of from 200 to 10000, for example from 500 to 5000
or from 800 to 1200 or from 850 to 1100, for example about
1000.
[0204] In these further aspects, the Mannich Base detergent is
obtainable by the reaction of at least one hydrocarbyl-substituted
hydroxyaromatic compound, at least one amine and at least one
aldehyde. The hydrocarbyl substituent of the aromatic group may be
or comprise polyisobutylene. 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.
[0205] The polyisobutylene amine and Mannich base detergents used
in these further aspects may also be as described elsewhere
herein.
[0206] The invention will now be described by way of example only
with reference to the following drawings, experiments and examples
in which examples according to the present invention are labelled
numerically as Example 1, Example 2 etc. and Experiments not
according to the present invention are labelled alphabetically as
Experiment A, Experiment B etc.
[0207] In the drawings FIGS. 1 and 2 represent in graph form,
clean-up performance versus additive treat rate (concentration) for
the fuel compositions tested.
[0208] 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 2.3 L
"Ranger" engine test) using a Ford 2.3 L port fuel injection
spark-ignition internal combustion engine.
[0209] The ASTM D-6201 cycle is as shown in Table 2:
TABLE-US-00002 TABLE 2 Manifold Absolute Engine Pressure (engine
load speed requirement) Duration Stage rpm kPa mmHg minutes Ramp
from (Transition) (Transition) (Transition) 0.5 0 to 2000 rpm
Steady state 2000 30.6 230 4 Ramp from (Transition) (Transition)
(Transition) 0.5 2000 to 2800 rpm Steady state 2800 71.8 540 8
For each evaluation firstly, 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.
[0210] 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.
[0211] "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 ]
##EQU00001##
An average of the values for the four valves was reported. The
higher the result (higher % "clean-up") the better the
performance.
Experiment A and B
[0212] The clean-up evaluation was assessed using a formulated E10
gasoline containing PIBA detergent additive at two different treat
rates (concentrations)--Experiments A and B.
[0213] The data are shown in Table 3 as relative % clean-up
(relative to clean-up of Experiment A) vs. treat rate (arbitrary
units). The data are shown in graph form in FIG. 1.
EXAMPLES 1, 2 & 3
[0214] Three different treat rates (concentrations) of a
combination of Mannich Base and polyisobutylene amine (with solvent
and carrier fluid) incorporated in an E 10 base fuel were assessed
for "clean-up" performance.
[0215] The data are shown in Table 3 as relative % clean-up
(relative to clean-up of Experiment A) vs. treat rate (arbitrary
units). The data are shown in graph form in FIG. 1.
TABLE-US-00003 TABLE 3 Concentration Clean up Arbitrary units (%
relative to clean-up of Experiment/Example (mass/volume) Experiment
A) Experiment A 3.52 100 Experiment B 5.70 204 Example 1 2.88 120
Example 2 3.57 138 Example 3 4.47 199
EXPERIMENTS C & D AND EXAMPLES 4, 5 & 6
[0216] Experiments A and B and Examples 1 to 3 were repeated using
a different E10 base fuel. The data are shown in Table 3 as
relative % clean-up (relative to clean-up of Experiment C) vs.
treat rate (arbitrary units). The data are shown in graph form in
FIG. 2.
TABLE-US-00004 TABLE 4 Concentration Clean up Arbitrary units (%
relative to clean-up of Experiment/Example (mass/volume) Experiment
C) Experiment C 3.52 100 Experiment D 5.70 137 Example 4 2.6 71
Example 5 2.88 62 Example 6 4.47 107
[0217] The data in Tables 3 and 4 and in FIGS. 1 and 2 show that
the fuel composition comprising in combination, at least one
Mannich Base detergent 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. The intake valve deposit clean-up performance
response is the rate at which the intake valve deposit clean-up
performance improves with an increase in treat rate. The gradients
for the Examples according to the invention are steeper than the
gradients for the PIBA detergent additive alone. Thus, the
invention permits a defined level of clean-up to be achieved at a
lower concentration of detergent additives.
[0218] Experiments were also conducted to assess the direct
injection fuel injector clean-up performance of a combination of
Mannich Base and polyisobutylene amine. Direct injection fuel
injector clean-up was observed.
[0219] These data illustrate a method of improving 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 which method comprises incorporating
into the fuel composition in one or more steps:
[0220] a. at least one Mannich Base detergent; and
[0221] b. at least one polyisobutylene amine
to produce a fuel composition which comprises said additives in
combination and which on combustion in a port fuel injection
spark-ignition engine produces greater intake valve deposit
clean-up performance than the intake valve clean-up performance
when combusting in said engine the fuel composition without said
combination of additives.
[0222] The data also illustrate the use as an intake valve deposit
clean-up additive in a fuel composition for a port fuel injection
spark-ignition internal combustion engine of a combination of:
[0223] a. at least one Mannich Base detergent; and
[0224] b. at least one polyisobutylene amine.
[0225] The data also illustrate a method of removing deposits from
the intake valves in a port fuel injection spark-ignition internal
combustion engine which method comprises supplying to the engine
through the port fuel injection intake valves, a fuel composition
which comprises a combination of:
[0226] a. at least one Mannich Base detergent; and
[0227] b. at least one polyisobutylene amine.
[0228] The data also illustrate that the intake valve deposit
clean-up performance of a fuel composition comprising a combination
of at least one Mannich Base detergent and at least one
polyisobutylene amine is improved relative to that of a fuel
composition which comprises at least one polyisobutylene amine, but
does not comprise at least one Mannich Base detergent. Accordingly,
in some examples, an additive composition comprising a combination
of:
[0229] a. at least one Mannich Base detergent; and
[0230] b. at least one polyisobutylene amine
is used for improving the intake valve deposit clean-up performance
response of a fuel composition in a port fuel injection
spark-ignition internal combustion engine as the treat rate of the
additive composition increases.
* * * * *