U.S. patent application number 10/521796 was filed with the patent office on 2006-05-18 for fuel composition.
This patent application is currently assigned to The Associated Octel Company Limited. Invention is credited to Stephen Leonard Cook, Matthew William Vincent, Keith Woodall.
Application Number | 20060101711 10/521796 |
Document ID | / |
Family ID | 9940947 |
Filed Date | 2006-05-18 |
United States Patent
Application |
20060101711 |
Kind Code |
A1 |
Vincent; Matthew William ;
et al. |
May 18, 2006 |
Fuel composition
Abstract
The present invention provides a fuel composition comprising a
fuel and a film-forming additive wherein the fuel comprises diesel
and a fuel alcohol and wherein the film-forming additive is present
in the fuel composition in an amount of less than 0.1 wt %.
Inventors: |
Vincent; Matthew William;
(Milton Keynes, GB) ; Cook; Stephen Leonard;
(Chester, GB) ; Woodall; Keith; (Bedfordshire,
GB) |
Correspondence
Address: |
NIXON PEABODY, LLP
401 9TH STREET, NW
SUITE 900
WASHINGTON
DC
20004-2128
US
|
Assignee: |
The Associated Octel Company
Limited
Global House, Bailey Lane
Manchester
GB
M90 4AA
|
Family ID: |
9940947 |
Appl. No.: |
10/521796 |
Filed: |
July 23, 2003 |
PCT Filed: |
July 23, 2003 |
PCT NO: |
PCT/GB03/03173 |
371 Date: |
December 29, 2005 |
Current U.S.
Class: |
44/436 |
Current CPC
Class: |
C10L 1/1881 20130101;
C10L 1/1985 20130101; C10L 1/1905 20130101; C10L 1/191 20130101;
C10L 1/2383 20130101; C10L 1/1883 20130101; C10L 1/221 20130101;
C10L 1/222 20130101; C10L 1/188 20130101; C10L 1/1826 20130101;
C10L 1/146 20130101; C10L 1/224 20130101; C10L 1/1852 20130101;
C10L 10/04 20130101; C10L 1/143 20130101; C10L 1/19 20130101; C10L
1/182 20130101; C10L 10/08 20130101 |
Class at
Publication: |
044/436 |
International
Class: |
C10L 1/18 20060101
C10L001/18 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 23, 2002 |
GB |
0217056.1 |
Claims
1. A fuel composition comprising: (i) a fuel; and (ii) a
film-forming additive; wherein the fuel comprises diesel and a fuel
alcohol; and wherein the film-forming additive is present in the
fuel composition in an amount of less than 0.1 wt %.
2. A fuel composition according to claim 1 wherein the film-forming
additive is present in the fuel composition in an amount of less
than 0.01 wt %.
3. A fuel composition according to claim 1 wherein the fuel alcohol
is present in the fuel in an amount of 1 to 30% by volume.
4. (canceled)
5. A fuel composition according to claim 1 wherein the fuel further
comprises a co-solvent.
6. The invention according to claim 5 wherein the co-solvent is an
alcohol.
7. A fuel composition according to claim 6 wherein the co-solvent
has the formula R.sup.1O(CH.sub.2CH.sub.2O).sub.nH, wherein n is a
number from 0 to 10 and R.sup.1 is a C.sub.1-30 hydrocarbyl
group.
8. A fuel composition according to claim 7 wherein the co-solvent
is selected from: (i) R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n
is 0 and R.sup.1 is ethylhexyl; and (ii)
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is from 2 to 3 and
R.sup.1 is a C.sub.5 to C.sub.15 alkyl.
9. A fuel composition according to claim 1 wherein the fuel further
comprises a surfactant.
10. A fuel composition according to claim 9 wherein the surfactant
has the formula R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2
wherein m is 0 or 1 and R.sup.2 is a C.sub.1-30 hydrocarbyl
group.
11. A fuel composition according to claim 10 wherein R.sup.2 is a
C.sub.8-22 hydrocarbon group.
12. A fuel composition according to claim 10 wherein the surfactant
is selected from: (i)
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
C.sub.18 alkenyl and m is 0; and (ii)
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
saturated or unsaturated C.sub.17 hydrocarbon and m is 1.
13. A fuel composition according to claim 9 claims wherein the fuel
further comprises a co-solvent of formula
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is 0 and R.sup.1 is
ethylhexyl; and a surfactant of formula
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
C.sub.18 alkenyl and m is 0.
14. A fuel composition according to claim 12 wherein the fuel
further comprises a co-solvent of formula
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is from 2 to 3 and
R.sup.1 is a C.sub.5 to C.sub.15 alkyl; and a surfactant of formula
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2is a
saturated or unsaturated C.sub.17 hydrocarbon and m is 1.
15. A fuel composition according to claim 1 wherein the
film-forming additive comprises a functional group selected from
the group consisting of a carboxylic acid, a carboxylic ester, an
alcohol, an amide and an amine.
16. A fuel composition according to claim 15 wherein the
film-forming additive is one or more compounds selected from the
group consisting of: (a) a C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group; (b) the
reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol; and/or (ii)
an amine; and/or (iii) an alcohol-amine; and/or (iv) an amino acid;
(c) a polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
17. A fuel composition according to claim 16 wherein the
C.sub.5-C.sub.100 hydrocarbyl is aliphatic.
18. A fuel composition according to claim 17 wherein the
C.sub.5-C.sub.100 hydrocarbyl is a C.sub.5-C.sub.100
hydrocarbon.
19. A fuel composition according to claim 18 wherein the
C.sub.5-C.sub.100 hydrocarbyl is a C.sub.5-C.sub.100 alkyl or
alkenyl.
20. A fuel composition according to claim 19 wherein the
film-forming additive is (a) a C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group having a
terminal carboxylic acid group.
21. A fuel composition according to claim 20 wherein the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group is linear.
22. A fuel composition according to claim 21 wherein the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group is selected from the group consisting of
lauric, myristic, myristoleic, palmitic, palmitoleic, stearic,
elaidic, oleic and linoleic acid.
23. A fuel composition according to claim 16 wherein the
film-forming additive is (a) a C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group and wherein the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group is substituted with at least two carboxylic
acid groups.
24. A fuel composition according to claim 23 wherein the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least two
carboxylic acid groups is a dimer-acid.
25. A fuel composition according to claim 23 wherein the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least two
carboxylic acid groups is derived from maleic acid, maleic
anhydride, succinic acid or succinic anhydride.
26. A fuel composition according to claim 23 wherein the
film-forming additive is the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with a reactive alcohol.
27. A fuel composition according to claim 26 wherein the reactive
alcohol is a diol, a triol or a polyol.
28. A fuel composition according to claim 27 wherein the reactive
alcohol is selected from the group consisting of ethylene glycol,
propylene glycol, butylene glycol, glycerol, pentaerythritol and
oligomers thereof.
29. A fuel composition according to claim 23 wherein the
film-forming additive is a compound of formula ##STR22## wherein
PIB is a polyisobutene group having an average molecular weight of
from 200 to 300 and R.sup.3 and R.sup.4 are independently selected
from --CH.sub.2CH.sub.2OH, --CH(CH.sub.3).sub.2, and H with the
proviso that R.sup.3 and R.sup.4 are not both H.
30. A fuel composition according to claim 29 either R.sup.3 and
R.sup.4 are both --CH.sub.2CH.sub.2OH or one of R.sup.3 and R.sup.4
is --CH.sub.2CH.sub.2OH and the other is --CH(CH.sub.3).sub.2.
31. A fuel composition according to claim 16 wherein the
film-forming additive is (c) a polymeric hydrocarbyl and the
polymeric hydrocarbyl is a polymer of C.sub.2-C.sub.10 hydrocarbon
monomers.
32. A fuel composition according to claim 31 wherein the polymeric
hydrocarbyl is a polymer of C.sub.2-C.sub.4 hydrocarbon
monomers.
33. A fuel composition according to claim 31 wherein the polymeric
hydrocarbyl is a primary alcohol.
34. A fuel composition according to claim 31 wherein the polymeric
hydrocarbyl is substituted with a group comprising an amide
group.
35. A fuel composition according to claim 16 wherein the
film-forming additive is (d) a substituted aromatic ring system
which is the product of a Mannich reaction.
36. A fuel composition according to claim 1 wherein the fuel
alcohol is an aliphatic alcohol.
37. A fuel composition according to claim 36 wherein the fuel
alcohol is an alkanol comprising an alkyl group and a hydroxy
group.
38. A fuel composition according to claim 37 wherein the alkyl
group is linear.
39. A fuel composition according to claim 1 wherein the fuel
alcohol is a C.sub.1-C.sub.10 alcohol.
40. A fuel composition according to claim 39 wherein the fuel
alcohol is a C.sub.1-C.sub.5 alcohol.
41. A fuel composition according to claim 40 wherein the fuel
alcohol is selected from methanol, ethanol, propanol, isopropanol,
and mixtures thereof.
42. A fuel composition according to claim 41 wherein the fuel
alcohol is ethanol.
43. A process for supplying a fuel composition to a combustion
engine wherein the process comprises (i) pumping the fuel
composition with a rotary pump to supply the fuel composition to
the combustion engine wherein the fuel composition comprises
diesel, a fuel alcohol and a film-forming additive.
44. A process according to claim 43 wherein the pumping step
supplies the fuel composition to the combustion engine at a rate
which under normal design operating conditions would result in
cavitation of the pump if operated with a fuel comprising diesel
and the fuel alcohol in the absence of the film-forming
additive.
45. A process according to claim 43 wherein the fuel composition
comprises: (i) a fuel comprising diesel, a fuel alcohol optionally
a co-solvent and optionally a surfactant; and (ii) less than 0.1 wt
% of a film-fonming additive.
46. (canceled)
47. (canceled)
48. (canceled)
49. A fuel composition according to claim 13 wherein the
film-forming additive is one or more compounds selected from the
group consisting of: (a) a C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group; (b) the
reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol; and/or (ii)
an amine; and/or (iii) an alcohol-amine; and/or (iv) an amino acid;
(c) a polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
50. A fuel composition according to claim 42 wherein the
film-forming additive is one or more compounds selected from the
group consisting of: (a) a C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group; (b) the
reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol; and/or (ii)
an amine; and/or (iii) an alcohol-amine; and/or (iv) an amino acid;
(c) a polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
51. A process according to claim 43 wherein the film-forming
additive is one or more compounds selected from the group
consisting of: (a) a C.sub.5-C.sub.100 hydrocarbyl substituted with
at least one carboxylic acid group; (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; (c) a
polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
52. A process for inhibiting and/or preventing cavitation in a fuel
and/or reducing the effects of cavitation in a fuel, wherein the
fuel comprises diesel and a fuel alcohol, comprising the step of
mixing the fuel with less than 0.1 wt % of a film-forming
additive.
53. A process according to claim 52 wherein the film-forming
additive is one or more compounds selected from the group
consisting of: (a) a C.sub.5-C.sub.100 hydrocarbyl substituted with
at least one carboxylic acid group; (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; (c) a
polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to fuel additives. In
particular the present invention relates to use of film-forming
additives to inhibit and/or prevent cavitation damage on pumping in
blends of fuel alcohol with diesel fuel.
BACKGROUND AND PRIOR ART
[0002] Internal combustion engines which function through the
medium of compression ignition, conventionally known as diesel
engines, are well known to those skilled in the art to generate a
significant level of particulate matter during the combustion
process. Diesel particulates are formed through the combustion or
pyrolysis of hydrocarbon fuels typically known as middle
distillates, and typically boiling in the temperature range
180.degree. C. to 360.degree. C. Particulates in the exhaust of a
diesel engine comprise inorganic ash due to engine wear particles
and the combustion products of lubricant oil additives, sulphur
containing compounds due to the sulphur in diesel fuel and
hydrocarbons from incomplete combustion. These hydrocarbons may be
further classified as either soluble material or solid matter, i.e.
carbonaceous soot. The soluble hydrocarbon portion of the
particulate matter will frequently be described by those skilled in
the art as the soluble organic fraction (SOF).
[0003] The particulate matter described above may comprise
particles so small as to be invisible to the naked eye. However,
diesel engines are also known to emit visible smoke, which
represents the obscuration of visible light by clouds of larger
particles. These larger particles, also called accumulation
particles, may arise from condensation and/or agglomeration of
smaller particles, also known as nucleation particles. The visual
impact which black exhaust smoke from diesel engine exhausts may
have on the beholder is almost universally negative. Black exhaust
smoke is perceived as a serious source of air pollution resulting
in damage to buildings and other property. In addition, all the
above-described particulate emissions are also widely understood to
represent a hazard to human health.
[0004] Governments in many countries have enacted legislation to
reduce permitted levels of particulate emissions from diesel
engines over recent years. Engine manufacturers have responded to
the legislation with the result that in many countries new diesel
engines consistently emit lower levels of exhaust particulate
matter than older engine designs. However one of the attractive
features of the diesel engine for operators and users is its
robustness and long life. Diesel engines may be in use for ten,
fifteen or twenty years, or, in exceptional cases, even longer.
These older engines, while providing very satisfactory service for
vehicle owners or operators, nevertheless continue to emit
pollutants, in particular particulates and visible smoke, at levels
at least as high as when new.
[0005] One option which is attractive to governments wishing to
improve air quality, is to alter fuel specifications so that all
vehicles, as opposed to merely the newer vehicles which are of
improved design, produce lower pollution levels. One way in which
this can be achieved, is to blend a fuel alcohol such as ethanol
into diesel fuel. A blend of ethanol and diesel is commonly known
as Ediesel.
[0006] The effect of Ediesel on exhaust emissions is subject to
some debate and is known to vary between engines of different
types. Nevertheless, the most pronounced effect is often found to
be in respect of particulate and smoke emissions, which are
frequently judged to be the most damaging pollutants emitted by
diesel engines. There is thus interest in blends of fuel alcohol
and diesel such as Ediesel in many countries of the world,
particularly where the diesel vehicle fleet comprises a significant
population of older vehicles with unacceptably high particulate
emissions.
[0007] An additional advantage provided by blends of a fuel alcohol
and diesel is the possibility of manufacturing the fuel alcohol, in
particular ethanol, initially from renewable products, including
waste products of agriculture. This capability provides the
opportunity to extend expensive fossil fuel sources, which often
need to be imported. Blending fuel alcohol produced from indigenous
and renewable sources into diesel fuel can thus make a major and
valued contribution to a nation's balance of payments.
[0008] The addition of a fuel alcohol to diesel is known to alter
the characteristics and physical properties of the base diesel
fuel. For example, ethanol boils at a much lower temperature than
diesel fuel, whose typical boiling range lies between 180.degree.
C. and 360.degree. C. When ethanol is added to diesel fuel, the
initial boiling point will be reduced very significantly. This is
illustrated in Table 1, which contains data obtained with middle
distillates alone and combined with ethanol. TABLE-US-00001 TABLE 1
Distillation characteristics of middle distillate fuels with and
without ethanol. ULSD3 ULSD3 + Kerosene + Distillation diesel 7.5%
vol. 7.5% vol characteristics fuel ethanol Kerosene ethanol Initial
boiling point .degree. C. 175.5 77.0 151.5 77.5 5% recovd. .degree.
C. 207.5 78.5 163.0 80.0 10% recovd .degree. C. 220.5 198.5 165.0
155.5 20% recovd .degree. C. 237.5 226.5 169.5 168.0 40% recovd
.degree. C. 262.5 255.0 179.0 175.0 70% recovd .degree. C. 297.5
294.5 197.0 195.5 90% recovd .degree. C. 330.5 332.5 216.5 216.0
Final boiling point .degree. C. 356.0 354.4 235.5 229.5
[0009] As is clear from the data in the table, the inclusion of a
relatively small volume of ethanol into either a conventional low
sulphur diesel fuel, or a kerosene fuel, produces a very
significant reduction in the initial boiling point and the 5-10%
recovered temperature values (also known as the "front end" by
those skilled in the art). Once the ethanol in the front end has
boiled off, the rest of the fuel behaves much like a similar base
fuel not containing ethanol, as would be expected.
[0010] In order to produce significant and readily-measured exhaust
emissions benefits, significant quantities, such as from about
1-30%, preferably 1-20% by volume of a fuel alcohol, such as
ethanol, are required. Where such substantial quantities of a fuel
alcohol, such as ethanol, are blended into a fuel the alcohol may
contain water and/or the composition may become hygroscopic. Diesel
fuels are well-known to encounter water during passage through the
supply chain. Whatever the source, the presence of water in the
fuel can lead to a phase-separation into aqueous and diesel fuel
phases with partition of the alcohol between the two. This is
particularly prone to occur at low temperatures and leads to
considerable operability problems.
[0011] To prevent such problems additional additives, such a
co-solvent(s) and surfactant(s) are employed. The amounts of each
used are, as expected, highly dependant on the particular fuel
alcohol, it's water content, anticipated ambient temperatures and,
above all, the volume percent alcohol in the fuel. In volume
percentage terms, the amounts of each used are-typically similar to
the volume percent alcohol and are each rarely less than 1%,
although quantities as low as 0.5, 0.2 or even 0.1 percent have
been claimed, where meaningful (i.e. detectably emissions-reducing)
quantities of alcohol are present. Where such levels of surfactant
are present, industry standard wear tests as hereinafter/before
described, indicate that no wear problems should be encountered
with that fuel.
[0012] The practical consequences of the change in fuel volatility
where a fuel alcohol is added to diesel fuel in diesel engine fuel
systems can be significant, since such fuel systems are usually
designed for the volatility characteristics of conventional middle
distillates. Diesel injection pumps, for example, function in such
a way that the film of fuel on various internal components may be
exposed to reduced pressure at times during each rotational cycle.
An example of this phenomenon is the contact between the slotted
face washer and the claws on the driver shaft which mate with it,
on the Bosch VE rotary diesel injection pump. During normal
operation, reduced pressure occurs in the region of the liquid film
on the surface of these components. With a conventional diesel fuel
or other middle distillate boiling between the ranges indicated in
Table 1, the local pressure reduction causes no operational
problems. However, with the much more volatile front end of the
fuel resulting from blending ethanol into diesel fuel, pressure
reduction in the liquid film is thought to produce cavitation.
[0013] Cavitation, as is known to those skilled in the art,
constitutes the formation and collapse of vapour-filled gas in
liquid bubbles associated with fluctuations in local pressure. It
is well known that prolonged cavitation can result in surface
damage to metallic components. Erosion of apparently hard metallic
surfaces is a characteristic feature of prolonged cavitation. Where
cavitation occurs in a diesel engine fuel system, for example in
the fuel injector pump, eroded particles, collectively called wear
debris, circulate within the pump. Such wear debris is frequently
abrasive. Circulation of wear debris within the pump accelerates
the wear process, while continuing cavitation produces further wear
debris, itself abrasive, leading to very accelerated wear in such
pumps. Examples of very accelerated wear in Bosch pumps through
cavitation, when operating on diesel fuel containing ethanol are in
the public domain. Bosch has publicised information on the Internet
(address www.mercosul.bosch.de/50 EPD/epd32), which not only
details accelerated wear in injector pumps, but also indicates
cavitation damage to other fuel injection equipment components,
such as injector needles and pump pressure valve seats. Similar
information has also been publicised in Hart's World Fuels Today on
14.sup.th November 2001.
[0014] The present invention alleviates the problems of the prior
art
STATEMENT OF INVENTION
[0015] According to a first aspect, the present invention provides
a fuel composition comprising a fuel and a film-forming additive
wherein the fuel comprises diesel and a fuel alcohol and wherein
the film-forming additive is present in the fuel composition in an
amount of less than 0.1 wt %.
[0016] According to a second aspect, the present invention provides
use of a film-forming additive for inhibiting and/or preventing
cavitation in a fuel and/or reducing the effects of cavitation in a
fuel, wherein the fuel comprises diesel and a fuel alcohol.
[0017] According to a third aspect, the present invention provides
a process for supplying a fuel composition to a combustion engine
wherein the process comprises (i) pumping the fuel composition with
a rotary pump to supply the fuel composition to the combustion
engine wherein the fuel composition comprises diesel, a fuel
alcohol and a film-forming additive.
[0018] It has surprisingly been found that film-forming additives
may be used to inhibit and/or prevent cavitation in blends of
diesel and a fuel alcohol. Addition of a film-forming additive to a
blend of diesel and a fuel alcohol may typically reduce the
cavitation-induced surface damage of metallic components in a
diesel engine fuel system in which the fuel blend is used.
Additionally, use of a film-forming additive in this manner may
reduce wear debris generated by cavitation and may also reduce the
wear to the diesel engine fuel system and in particular the fuel
injection equipment which the wear debris may cause. Thus, use of a
film-forming additive according to the present invention, may
increase the lifetime of the diesel engine fuel system especially
fuel injection equipment components, such as fuel injector pumps,
injector needles and pump pressure seat valves.
[0019] The recent discovery that fuels containing fuel alcohols
could cause damage to diesel engine components was, indeed,
surprising. More so was that such fuels could satisfy
industry-standard wear tests yet give in-service problems. It has
surprisingly been found that film-forming additives may be used to
protect engine components from such wear. Without wishing to be
bound by theory it is believed that they act to inhibit and/or
prevent cavitation in blends comprising diesel and a fuel
alcohol
[0020] The term "film-forming additive" as used herein, means a
substance which, when present in a fuel composition comprising a
fuel, the film-forming additive and optional further fuel
components, increases the ability of the fuel to form a coating on
a metal surface, such as a metal surface within a fuel pump, with
which it is contacted.
[0021] Particularly useful as a film-forming additive according to
the present invention is a substance capable of providing a fuel
with which it is contacted with a fuel quality parameter whereby
wear between two metal surfaces in contact with each other and with
the fuel in a test apparatus is limited to a permitted maximum
level. Limitation of wear in a test apparatus may be determined by
exceeding a minimum applied load of greater than 2800 g, as in the
Scuffing Load Ball-On-Cylinder Lubricity Evaluator method
(SLBOCLE--ASTM D 6078). Alternatively, limitation of wear in a test
apparatus may be determined by not exceeding a wear limit, as in
the High Frequency Reciprocation Rig method (HFRR-ASTM D 6079) of
460 micron wear scar diameter (WSD) at 60.degree. C. Limitation of
wear may also be measured using the HFRR equipment under the
Coordinating European Council (CEC) F-06-A-96 method, which is very
similar to the ASTM D 6079 method, but embodies additional controls
on temperature and humidity, and may therefore be expected to
provide greater test precision than ASTM D 6079.
[0022] The term "cavitation" as used herein means the rapid
formation and collapse of vapour pockets in a liquid in regions of
locally fluctuating pressure.
[0023] Without wishing to be bound by theory it is believed that
the film-forming additive may inhibit and/or prevent cavitation
according to the present invention in one or more of the following
ways.
[0024] The film-forming additive may provide a sacrificial layer on
the surface of the components exposed to cavitation, such that
material is removed from the sacrificial layer rather than from the
metallic surface covered and protected by the sacrificial layer of
film-forming additive.
[0025] Replenishment of the sacrificial layer may be provided by
the supply of fresh additised fuel according to the present
invention to the potentially wearing components. Protection for the
metal surfaces of vulnerable components by the sacrificial layer
may prevent wear debris from forming and circulating, for example
within the injector pump. Furthermore, since the film-forming
additive does not itself create abrasive particles, removal of
parts of the protective sacrificial layer of film-forming additive
by the process of cavitation will not subsequently lead to
accelerated wear within diesel engine fuel systems and in
particular within fuel pumps. Therefore use of a film-forming
additive according to the present invention may provide protection
from the effects of cavitation resulting from the inclusion of a
fuel alcohol in diesel as typified by blends such as Ediesel.
[0026] Alternatively, or additionally, the existence of a
protective film at the metal surface, whether monolayer or
(particularly) multilayer may preclude the possibility of
vapour-filled bubble formation in the vicinity of that surface.
Fuel alcohols, in particular ethanol, are known to have limited
solubility in diesel fuel. The fuel alcohol may thus have a limited
solubility in the boundary layer film, which itself is highly
compatible with diesel fuel. Further, higher concentrations of fuel
alcohol in diesel are typically obtained using surfactant
co-additives. In such cases the fuel alcohol may be thought of as
maintained as a suspension of droplets sheathed by surfactant
co-additive. On the molecular scale, these can be large assemblies
and so physically unable to penetrate any protective film. Thus,
the volatile component associated with the onset of cavitation may
be physically separated from the metal surface. Vapour-filled
bubbles formed during cavitation may similarly form remote from the
surface and so not remove material from it either by plucking or
jetting mechanisms.
[0027] A further alternative or additional effect according to the
present invention, may be the passivating of freshly-exposed
surfaces. Cavitation by ultrasound is well-known for cleaning of
metal and other hard surfaces. Enhanced chemical reactivity of
metals towards organic species under the influence of power
ultrasound is well-known and frequently ascribed to removal of
passivating surface oxide or insoluble reaction products. Ediesel
and other alcohol-containing diesel fuel blends are widely
understood to be more corrosive towards fuel delivery systems than
the diesel base fuels. Thus cavitation can lead to exposure of
fresh, highly-reactive metal surface to the alcohol containing
fuel. The films formed on the metal surface may thus prevent access
of the corrosive components to the freshly-exposed surface, and
thereby reduce or prevent corrosion.
[0028] In yet a further alternative or additional effect, the
mechanical grinding action of wear particles within the boundary
layer is thought to be responsible for at least some additional
wear. Film-forming substances may form films on both the residual
surface and the wear particle and so provide boundary lubrication
layers on both bodies. This may act to keep the wear-particle in
suspension and so ultimately remove it from the metal surface, or
at the least act as a lubricant film to prevent scuffing or other
wear.
[0029] For ease of reference these and further aspects of the
present invention are now discussed under appropriate section
headings. However, the teachings under each section are not
necessarily limited to each particular section.
PREFERRED EMBODIMENTS
[0030] As previously mentioned, in one aspect, the present
invention provides a fuel composition comprising a fuel and a
film-forming additive wherein the fuel comprises diesel and a fuel
alcohol and wherein the film-forming additive is present in the
fuel composition in an amount of less than 0.1 wt %.
[0031] As previously mentioned, in a further aspect, the present
invention provides use of a film-forming additive for inhibiting
and/or preventing cavitation in a fuel and/or reducing the effects
of cavitation in a fuel, wherein the fuel comprises diesel and a
fuel alcohol.
[0032] In a preferred aspect, the film-forming additive is present
in an amount of less than 0.01 wt %.
[0033] The film-forming additive may be employed at treat rates of
up to or less than 0.1 wt %, such as up to or less than 0.08 wt %,
such as up to or less than 0.07 wt %, such as up to or less than
0.05 wt %, such as up to or less than 0.04 wt %, such as up to or
less than 0.03 wt %, such as up to or less than 0.02 wt %, such as
up to or less than 0.01 wt %, preferred treat rates being 10-1,000
ppm e.g. 800 ppm. Particularly preferred treat rates are 50-500 ppm
and most preferred 100-300 ppm. In all cases ppm refers to mg
film-forming additive per kg fuel.
Fuel
[0034] As previously mentioned, the fuel comprises diesel and a
fuel alcohol.
Fuel Alcohol
[0035] Preferably the fuel alcohol is present in the fuel in an
amount of 1 to 30% by volume, preferably 1 to 20%, such as 1 to
15%, 2 to 15% or 3 to 15%.
[0036] Preferably the fuel alcohol is an aliphatic alcohol.
[0037] Preferably the fuel alcohol is an alkanol comprising an
alkyl group and a hydroxy group. More preferably the fuel alcohol
is an alkanol comprising a linear alkyl group and a hydroxy
group.
[0038] Preferably the fuel alcohol is a C.sub.1-C.sub.20 alcohol
such as a C.sub.1-C.sub.15 alcohol or a C.sub.1-C.sub.10 alcohol.
Preferably the fuel alcohol is a C.sub.1-C.sub.5 alcohol such as an
alcohol selected from methanol, ethanol , propanol and
iso-propanol.
[0039] In a particularly preferred aspect the fuel alcohol is
ethanol.
[0040] Preferably the ethanol is distilled prior to blending with
the diesel. The ethanol used is typically, but not by way of
limitation, at least 90% preferably 95% and even more preferably at
least 96% anhydrous ethanol.
Additional Components
[0041] The fuel composition may additionally comprise one or more
additives. Examples of such additives include surfactants such as
emulsifiers, stabilising additives and co-solvents.
[0042] The inclusion in the fuel of fuel alcohol, which may not be
anhydrous, may typically result in the inclusion of water and it is
well known that an additional minor component may be added to the
fuel blend as a co-solvent to stabilise the blend of fuel alcohol
and diesel fuel. Without such a component, under certain conditions
water is prone to separate out and the alcohol to partition between
aqueous and fuel phases.
Co-Solvent
[0043] In one preferred aspect the fuel further comprises a
co-solvent.
[0044] A suitable co-solvent may be selected from the group
consisting of alkyl alcohols having a hydrocarbon chain length of
about three to about six, inclusive, such as tertiary butyl
alcohol, for example; naphtha; .gamma.-valerolactone; kerosene;
hydrocarbons having a chain length of greater than about 50; and
mixtures thereof.
[0045] Preferably the co-solvent is an alcohol. More preferably the
co-solvent has the formula R.sup.1O(CH.sub.2CH.sub.2O).sub.nH,
wherein n is a number from 0 to 10 and R.sup.1 is a C.sub.1-30
hydrocarbyl group.
[0046] As used herein, the term "hydrocarbyl" refers to a group
comprising at least C and H that may optionally comprise one or
more other suitable substituents. Examples of such substituents may
include halo-, alkoxy-, nitro-, an alkyl group, or a cyclic group.
In addition to the possibility of the substituents being a cyclic
group, a combination of substituents may form a cyclic group. If
the hydrocarbyl group comprises more than one C then those carbons
need not necessarily be linked to each other. For example, at least
two of the carbons may be linked via a suitable element or group.
Thus, the hydrocarbyl group may contain heteroatoms. Suitable
heteroatoms will be apparent to those skilled in the art and
include, especially nitrogen and oxygen.
[0047] In a preferred aspect, R.sup.1 is a hydrocarbon group.
[0048] As used herein the term "hydrocarbon" means any one of an
alkyl group, an alkenyl group, an alkynyl group and an acyl group,
which groups may be linear, branched or cyclic, or an aryl group.
The term hydrocarbon also includes those groups but wherein they
have been optionally substituted. If the hydrocarbon is a branched
structure having substituent(s) thereon, then the substitution may
be on either the hydrocarbon backbone or on the branch;
alternatively the substitutions may be on the hydrocarbon backbone
and on the branch.
[0049] In a highly preferred aspect, R.sup.1is an alkyl group. In
this aspect, R.sup.1 may be linear or branched. In this aspect,
R.sup.1 may be saturated or unsaturated.
[0050] Preferably n is a number from 0 to 5. In one preferred
aspect, n is 0. In another preferred aspect, n is a number from 2
to 4, preferably a number from 2 to 3, more preferably n is about
2.75.
[0051] In one embodiment, the co-solvent is
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is 0.
[0052] In this embodiment preferably R.sup.1 is a C.sub.5 to
C.sub.15 alkyl, preferably C.sub.5 to C.sub.15 alkyl, more
preferably C.sub.8 alkyl. One preferred co-solvent is
2-ethylhexanol: ##STR1##
[0053] In another embodiment, the co-solvent is
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is greater than 0.
[0054] Preferred co-solvents are alkoxylated alcohols, preferably
ethoxylated alcohols. It is highly preferable that the ethoxylated
alcohols are oil soluble alcohols. Therefore, alkanols are
preferred and these may be primary, secondary or tertiary alkanols
and especially primary alkanols. As the oil solubility of the
alcohol may vary with the carbon chain length of the ethoxylated
alkanol, the alkanol is preferably a C.sub.5 to C.sub.22 alkanol,
more preferably C.sub.5 to C.sub.15 alkanol. The ethoxylated
alcohol may comprise a mixture of alkanols. However, it is
preferred that in such mixtures one alkanol will predominate. Thus,
the most preferred alkanol is predominantly a C.sub.5 to C.sub.15
alkanol. In addition the degree of ethoxylation of the alcohol may
be varied and the oil solubility will, generally, decrease with the
increase in the degree of ethoxylation. It is preferred that the
ethoxylate to alcohol ratio is greater than 2. More preferably, the
ethoxylate to alcohol ratio is from between 1 and 10, preferably
between 1 and 5, more preferably between 1 and 3 and especially
between 2 and 3. A commercially available ethoxylated alcohol is
especially preferred in which the ethoxylate to alcohol ratio is
2.75. Such an alcohol ethoxylate is available as NEODOL 91/2.5.
[0055] Thus, in this preferred embodiment, the co-solvent is
R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is a number from 2
to4, preferably a number from 2 to 3, more preferably n is about
2.75. In this embodiment, preferably R.sup.1 is a C.sub.5 to
C.sub.15 alkyl.
Surfactant
[0056] In another preferred aspect the fuel further comprises a
surfactant. Preferably the surfactant is an emulsifier.
[0057] Examples of suitable surfactants include [0058] amides of
long-chain (C.sub.10-C.sub.30) fatty acids prepared from
dialkylaminoalcohols such as dimethylaminoethanol as exemplified in
U.S. Pat. No. 4,451,265; [0059] Ammonium salts prepared by reaction
of long chain fatty acids with lower trialkylamines as set out in
U.S. Pat. No. 4,451,267; [0060] diesel soluble ethylene
oxide/styrene block copolymers, coupled by styrene/butadiene as in
U.S. Pat. No. 4,482,666; [0061] 1:2:3 mixtures of sorbitan
sesquioleate, polyethylene glycol monoleate and nonylphenol
ethoxylate as claimed in WO-A-97/34969; [0062] reaction product of
phthallic (or other monobasic carboxylic) acid+poly(amine)+second
carboxylic acid in the ratio 1/no. of equivalents of first acid:
2/no. of amine groups of polyamine:l/no. of equivalents of second
acid as exemplified by EP-A-0386550; [0063] 93-97% sbrbitan fatty
acid monoester and 3-7 wt % polysorbate 80 as found in AU 563,404;
[0064] oleyldiethanolamide, diethanolamine and diethanolamine soap
of oleic acid which has been treated with about 0-7% of oleic acid
as discussed in U.S. Pat. No. -4,173,455; and [0065] C8-C.sub.22
fatty acids as polyglycerol esters, sorbitan esters or diacetyl
tartaric acid esters of glycerol esters of the said fatty acids as
discussed in DE 2,229,918.
[0066] In a preferred aspect, the surfactant has the formula
R.sup.2(CO).sub.m--N([CH.sub.2].sub.1-10OH).sub.2 wherein m is 0 or
1 and R.sup.2 is a C.sub.1-30 hydrocarbyl group.
[0067] In a preferred aspect, the surfactant has the formula
R.sup.2(CO).sub.m--N([CH.sub.2].sub.1-3OH).sub.2 wherein m is 0 or
1 and R.sup.2 is a C.sub.1-30 hydrocarbyl group.
[0068] In a preferred aspect, the surfactant has the formula
R.sup.2(CO).sub.m--N([CH.sub.2].sub.1-3OH).sub.2 wherein m is 0 or
1 and R.sup.2 is a C.sub.1-30 hydrocarbyl group.
[0069] In a preferred aspect, the surfactant has the formula
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein m is 0 or 1
and R.sup.2 is a C.sub.1-30 hydrocarbyl group.
[0070] Preferably R.sup.2 is a hydrocarbon group. More preferably
R.sup.2 is an alkyl group or an alkenyl group. In this aspect,
R.sup.2 may be linear or branched. In this aspect, R.sup.2 may be
saturated or unsaturated.
[0071] Preferably R.sup.2 is a C.sub.8-22 hydrocarbyl group, more
preferably a C.sub.8-22 hydrocarbon group, such as a C.sub.8-22
alkyl group or a C.sub.8-22 alkenyl group.
[0072] Preferably R.sup.2 is a C.sub.10-20 hydrocarbyl group, more
preferably a C.sub.10-20 hydrocarbon group, such as a C.sub.10-20
alkyl group or a C.sub.10-20 alkenyl group.
[0073] Preferably R.sup.2 is a C.sub.12-20 hydrocarbyl group, more
preferably a C.sub.12-20 hydrocarbon group, such as a C.sub.12-20
alkyl group or a C.sub.12-20 alkenyl group.
[0074] Preferably R.sup.2 is a C.sub.12-20 hydrocarbyl group, more
preferably a C.sub.14-18 hydrocarbon group, such as a C.sub.14-18
alkyl group or a C.sub.14-18 alkenyl group.
[0075] In one embodiment, m is 0. Thus the surfactant has a formula
R.sup.2N([CH.sub.2].sub.1-10OH).sub.2, preferably
R.sup.2N([CH.sub.2].sub.1-5OH).sub.2, preferably
R.sup.2N([CH.sub.2].sub.1-3OH).sub.2, preferably
R.sup.2N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a C.sub.1-30
hydrocarbyl group. In this aspect, preferably R.sup.2 is a
C.sub.8-22 hydrocarbon, such as a C.sub.16-20 hydrocarbon, more
preferably a C.sub.18 hydrocarbon. In this aspect, preferably
R.sup.2 is unsaturated, more preferably R.sup.2 is an alkenyl.
Preferably R.sup.2 is an unsaturated C.sub.18 hydrocarbon, more
preferably a C.sub.18 alkenyl, most preferably an oleyl group.
[0076] In another embodiment m is 1. Thus the surfactant has a
formula R.sup.2(CO)--N([CH.sub.2].sub.1-10OH).sub.2, preferably
R.sup.2(CO)--N([CH.sub.2].sub.1-5OH).sub.2, preferably
R.sup.2(CO)--N([CH.sub.2].sub.1-3OH).sub.2, preferably
R.sup.2(CO)--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
C.sub.1-30 hydrocarbyl group. In this aspect, preferably R.sup.2 is
a C.sub.7-21 hydrocarbon, such as a C.sub.15-19 hydrocarbon, more
preferably a C.sub.17 ydrocarbon: In this aspect R.sup.2 may be
saturated or unsaturated. Preferably R.sup.2.is a C.sub.7-21,
alkyl, such as a C.sub.15-19 alkyl, more preferably a C.sub.17
alkyl.
Co-Solvent Surfactant Systems
[0077] In a highly preferred aspect, the fuel further comprises a
co-solvent and a surfactant.
[0078] In one preferred aspect, the fuel further comprises a
co-solvent of formula R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n
is 0 and R.sup.1 is ethylhexyl; and a surfactant of formula
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
C,8 alkenyl and m is 0.
[0079] Preferably the fuel further comprises 2ethylhexanol and a
surfactant of formula R.sup.2N(CH.sub.2CH.sub.2OH).sub.2 wherein
R.sup.2 is an oleyl group.
[0080] In another preferred aspect, the fuel further comprises a
co-solvent of formula R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n
is from 2 to 3 and R.sup.1 is a C.sub.5 to C.sub.15 alkyl; and a
surfactant of formula
R.sup.2(CO).sub.m--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is a
saturated or unsaturated C.sub.17 hydrocarbon and m is 1.
[0081] Preferably the fuel further comprises a co-solvent of
formula R.sup.1O(CH.sub.2CH.sub.2O).sub.nH wherein n is about 2.75
and R.sup.1is a C.sub.5 to C.sub.15 alkyl; and a surfactant of
formula R.sup.2(CO)--N(CH.sub.2CH.sub.2OH).sub.2 wherein R.sup.2 is
a C.sub.17 alkyl.
[0082] Preferred surfactant systems include C.sub.8-C.sub.22 acid
diethanolamides, e.g. C.sub.12 acid diethanolamides, preferably
C.sub.18 diethanolamide and fatty acid ethoxylates of
C.sub.8-C.sub.22 acids, e.g. C.sub.12, preferably C.sub.18 with
1-12, preferably 2-10, most preferably about 7 ethoxy groups. A
particularly preferred system is 1:1:2 mixture of these two
components with the preferred alcohol ethoxylate cosolvent.
[0083] It will be readily understood that when a co-solvent is
present, the co-solvent is different from the film-forming
additive.
[0084] It will be readily understood that when a surfactant is
present, the surfactant is different from the film-forming
additive.
[0085] It will be readily understood that when a co-solvent and a
surfactant are present, the co-solvent is different from the
surfactant.
[0086] The co-solvent is typically present in an amount of more
than 0.1 wt %. The surfactant is typically present in an amount of
more than 0.1 wt %.
Film-Forming Additive
[0087] In one aspect, the film-forming additive comprises a
functional group selected from the group consisting of a carboxylic
acid, a carboxylic ester, an alcohol, an amide and an amine.
[0088] Preferably, the film-forming additive comprises a functional
group selected from the group consisting of a carboxylic acid, a
carboxylic ester and an alcohol.
[0089] In one embodiment, preferably the film-forming additive
comprises a carboxylic acid.
[0090] In one embodiment, preferably the film-forming additive
comprises a carboxylic ester group.
[0091] In one embodiment, preferably the film-forming additive
comprises an alcohol group.
[0092] Preferably, the film-forming additive comprises a carboxylic
ester group and an alcohol group.
[0093] In a preferred aspect, the film-forming additive is one or
more compounds selected from the group consisting of (a) a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group; (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; (c) a
polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
[0094] As used herein, the term "hydrocarbyl" refers to a group
comprising at least C and H that may optionally comprise one or
more other suitable substituents. Examples of such substituents may
include halo-, alkoxy-, nitro-, an alkyl group, or a cyclic group.
In addition to the possibility of the substituents being a cyclic
group, a combination of substituents may form a cyclic group. If
the hydrocarbyl group comprises more than one C then those carbons
need not necessarily be linked to each other. For example, at least
two of the carbons may be linked via a suitable element or group.
Thus, the hydrocarbyl group may contain heteroatoms. Suitable
heteroatoms will be apparent to those skilled in the art and
include, especially nitrogen and oxygen.
[0095] In one aspect preferably the hydrocarbyl group is free of
sulphur.
[0096] As used herein the term "hydrocarbon" means any one of an
alkyl group, an alkenyl group, an alkynyl group and an acyl group,
which groups may be linear, branched or cyclic, or an aryl group.
The term hydrocarbon also includes those groups but wherein they
have been optionally substituted. If the hydrocarbon is a branched
structure having substituent(s) thereon, then the substitution may
be on either the hydrocarbon backbone or on the branch;
alternatively the substitutions may be on the hydrocarbon backbone
and on the branch.
(a) C.sub.5-C.sub.100 Hydrocarbyl and (b) Reaction Product of
C.sub.5-C.sub.100 Hydrocarbyl
[0097] Preferably, the film-forming additive is one or more
compounds selected from the group consisting of (a) a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group; and (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid.
C.sub.5-C.sub.100 Hydrocarbyl
[0098] Preferably the C.sub.5-C.sub.100 hydrocarbyl is a
C.sub.5-C.sub.80 hydrocarbyl group such as a C.sub.5-C.sub.50
group, a C.sub.5-C.sub.40 group or a C.sub.5-C.sub.30 group. More
preferably the C.sub.5-C.sub.100 hydrocarbyl is a C.sub.5-C.sub.20
group such as a C.sub.10-C.sub.20 group or a C.sub.12-C.sub.18
group in particular a C.sub.12 C14 C.sub.16, or C.sub.18 group.
[0099] Preferably the C.sub.5-C.sub.100 hydrocarbyl is aliphatic,
more preferably it is a C.sub.5-C.sub.100 hydrocarbon, more
preferably a C.sub.5-C.sub.100 alkyl or alkenyl.
[0100] According to one preferred embodiment, the C.sub.5C.sub.100
hydrocarbyl substituted with at least one carboxylic acid group
comprises a terminal carboxylic acid group.
[0101] In this aspect, preferably the C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group is linear.
[0102] In this aspect, preferably the C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group is selected
from the group consisting of lauric, myristic, myristoleic,
palmitic, palmitoleic, stearic, elaidic, oleic and linoleic
acid.
[0103] Examples of suitable compounds include natural and synthetic
fatty acids as well as the mixtures and impure fractions thereof
such as tall-oil fatty acids, tallow oils, palm oil, rape-seed oil
and the like.
[0104] According to another preferred embodiment, the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group is substituted with at least two carboxylic
acid groups.
[0105] In this aspect, preferably the C.sub.5-C.sub.100 hydrocarbyl
substituted with at least two carboxylic acid groups is a
dimer-acid.
[0106] The term "dimer-acid" as used herein means the dimerisation
product of two unsaturated C.sub.5-C.sub.100 hydrocarbyls each
substituted with at least one carboxylic acid group.
[0107] Examples of preferred dimer-acids include the dimerisation
products of two linear alkenyl groups each substituted with at
least one carboxylic acid group, preferably at least one terminal
carboxylic acid group. Particularly preferred is dimerised linoleic
acid such as DCI 4A available from The Associated Octel Company,
UK.
[0108] Alternatively, in this aspect, preferably the
C.sub.5-C.sub.100 hydrocarbyl substituted with at least two
carboxylic acid groups is derived from maleic acid, maleic
anhydride, succinic acid, or succinic anhydride.
[0109] Examples of suitable compounds include alkyl- or alkenyl
succinic acids. These materials may be formed via the reaction of
maleic anhydride with alkenes. Typically, alkenes suitable for use
in such reactions are obtained by the oligomerisation of low
molecular weight olefin streams, such as ethylene, propylene and
butylenes, including both 2-methylpropene and mixed
C.sub.4-monoolefin streams. The double bond in the oligomer may be
terminal (vinylic), di- or tri-substituted or may, as is
particularly the case for oligomers from the C.sub.4 olefin stream,
comprise mixtures thereof: Suitable olefins derived from ethylene
include dodec-1-ene, octadec-1-ene and the mixed internal olefins
obtained by isomerisation thereof. A suitable olefin derived from
propene would be tetrapropene. Suitable olefins derived from
C.sub.4-olefins include the so-called poly(butenes), characterised
by their number average molecular weight. An example of a suitable
such olefin would be BP-Amoco Indopol L-6, which has a number
average molecular weight of 260. The reaction between the olefin
and maleic acid may be carried out by the so-called "thermal route"
resulting in a succinate substituted at the .alpha.-position to
only one carboxyl group or via the "chlorine route" resulting in a
succinate substituted .alpha.- to each carboxyl group and
comprising part of a six-membered ring structure. The succinates
may also be hydrogenated to substantially convert the
alkenyl-succinates to alkyl-succinates.
[0110] Preferably the C.sub.5-C.sub.100 hydrocarbyl comprising at
least one carboxylic anhydride group is derived from maleic acid,
maleic anhydride, succinic acid, or succinic anhydride.
(b) Reaction Product of C.sub.5-C.sub.100 Hydrocarbyl
[0111] In a preferred aspect, the film-forming additive is (b) the
reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol; and/or (ii)
an amine; and/or (iii) an alcohol-amine; and/or (iv) an amino
acid.
[0112] Preferably the C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group is as herein described.
[0113] More preferably the C.sub.5-C.sub.100 hydrocarbyl
substituted with at least one carboxylic acid group or comprising
at least one carboxylic anhydride group is derived from maleic
acid, maleic anhydride, succinic acid or succinic anhydride.
Reactive Alcohol
[0114] The reactive alcohol may be a mono-alcohol, a diol, a triol
or a polyol. Preferably the reactive alcohol is a diol, a triol or
a polyol.
[0115] More preferably the reactive alcohol is selected from the
group consisting of ethylene glycol, propylene glycol, butylene
glycol, glycerol, pentaerythritol and oligomers thereof.
[0116] In one preferred embodiment, the reactive alcohol is
1-aza-3,7-dioxabicyclo [3.3.0]-oct-5-yl methyl alcohol.
[0117] In a preferred aspect the film-forming additive is (b) the
reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol.
[0118] Particularly suitable as a film-forming additive according
to the present invention are the esters of mono-, di-, tri- and
poly(hydroxy) alcohols with natural and synthetic long chain fatty
acids particularly those in which there is an excess of hydroxyl
groups to carboxylic acid groups. For example, a diol may be
reacted with a mono-carboxylic acid to provide products containing
in excess of two molecules of acid per molecule of alcohol, up to
the theoretical maximum of one acid per alcohol.
[0119] Various esters of the succinates as previously described are
also suitable as film-forming additives according to the present
invention. For example the hemi-esters with mono-alcohols, such as
in particular propan-2-ol, or with polyhydric alcohols as herein
described. Alternatively, mixed-esters of the above succinates with
a mono-alcohol and a polyhydric alcohol may be used. For example, a
succinate ester of propan-2-ol with ethylene glycol. Finally, the
esters of succinates as described above with poly(hydric) alcohols
may be used.
[0120] In a preferred aspect the film-forming additive is a
compound of formula ##STR2## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0121] In a preferred aspect the film-forming additive is a
compound of formula ##STR3## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from (C1-5 straight or
branched alkyl)OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0122] In a preferred aspect the film-forming additive is a
compound of formula ##STR4## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from (C1-3 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0123] In a preferred aspect the film-forming additive is a
compound of formula ##STR5## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0124] In a preferred aspect the film-forming additive is a
compound of formula ##STR6## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0125] In a preferred aspect the film-forming additive is a
compound of formula ##STR7## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 800 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0126] In a preferred aspect the film-forming additive is a
compound of formula ##STR8## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 600 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0127] In a preferred aspect the film-forming additive is a
compound of formula ##STR9## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 400 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0128] In a preferred aspect the film-forming additive is a
compound of formula ##STR10## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 300 and R.sup.3
and R.sup.4 are independently selected from (C1-10 straight or
branched alkyl)-OH, and H with the proviso that R.sup.3 and R.sup.4
are not both H.
[0129] In a highly preferred aspect the film-forming additive is a
compound of formula ##STR11## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 1000 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0130] In a highly preferred aspect the film-forming additive is a
compound of formula ##STR12## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 800 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0131] In a highly preferred aspect the film-forming additive is a
compound of formula ##STR13## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 600 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0132] In a highly preferred aspect the film-forming additive is a
compound of formula ##STR14## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 400 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0133] In a highly preferred aspect the film-forming additive is a
compound of formula ##STR15## wherein PIB is a polyisobutene group
having an average molecular weight of from 200 to 300 and R.sup.3
and R.sup.4 are independently selected from --CH.sub.2CH.sub.2OH,
--CH(CH.sub.3).sub.2, and H with the proviso that R.sup.3 and
R.sup.4 are not both H.
[0134] In one preferred embodiment, R.sup.3 and R.sup.4 are both
--CH.sub.2CH.sub.2OH and the film-forming additive is a compound of
formula ##STR16##
[0135] In another preferred embodiment one of R.sup.3 and R.sup.4
is --CH.sub.2CH.sub.2OH and the other is --CH(CH.sub.3).sub.2 and
the film-forming additive is a compound of formula ##STR17## or a
mixture thereof.
[0136] In a preferred aspect PIB is a polyisobutene group having an
average molecular weight of about 260.
[0137] Further preferred film-forming additives are TABLE-US-00002
Additive 1 Dimerised linoleic acid 2 ##STR18## PIB is a
poly(butene) of number average molecular weight 260, R.sup.3 and
R.sup.4 are both --CH.sub.2CH.sub.2OH. 3 ##STR19## PIB is a
poly(butene) of number average molecular weight 260 R.sup.3 and
R.sup.4 are each independently --CH.sub.2CH.sub.2OH or
--CH(CH.sub.3).sub.2 and are in substantially 1:1 molar ratio
overall. 4 ##STR20## PIB is a poly(butene) of number average
molecular weight 260 one of R.sup.3 and R.sup.4 is H or
--CH(CH.sub.3).sub.2 and the other of R.sup.3 and R.sup.4 is H,
--CH(CH.sub.3).sub.2 or --CH.sub.2CH.sub.2OH, provided that R.sup.3
and R.sup.4 are not both H.
Amine
[0138] The amine may be any suitable substituted or unsubstituted
amine. If the amine is substituted it may typically be substituted
with a hydrocarbon group, preferably an alkyl group. However,
examples of suitable substituted amines include guanidine,
aminoguanidine, urea, thiourea and salts thereof. Suitable amines
also include polyamines and poly(piperidine).
Alcohol-Amine
[0139] The alcohol-amines which are particularly suitable include
secondary alcohol-amines for example aminoethyl ethanolamine and
polyhydric alcohol-amines such as di-alkanolamines, in particular
di-ethanolamine; and primary alcohol-amines.
Amino Acid
[0140] Preferably the amino-acid is a primary amino acid. More
preferably the amino acid is a .alpha.,.omega.-primary
amino-acid.
Reactions
[0141] The reactions with (i) a reactive alcohol; and/or (ii) an
amine; and/or (iii) an alcohol-amine; and/or (iv) an amino acid may
be carried out stepwise or alternatively the reactions may be
carried out simultaneously in a single reaction vessel. If the
reactions are carried out stepwise they may be carried out in any
order.
[0142] Examples of suitable film-forming additives according to
this aspect of the present invention include amides or mixtures of
ester and amide which may be prepared by reaction of any of the
above-described carboxylic or succinic anhydrides, acids or
hemi-esters with poly(hydric) alcohol-amines, such as, for example,
di-ethanolamine.
[0143] Also suitable are mixed amides of the succinates which may
be prepared by stepwise reaction of the succinic anhydride or
succinic acid with secondary amine or secondary alcohol-amines
followed by poly(amine), poly(piperidine) or alkoxyamine. The
stepwise reactions may be carried out in any order.
[0144] Succinates prepared as herein described may also be
converted into succinimides of utility in the current application
by reaction with alcohol-amines containing at least one primary
amine group.
[0145] Alkyl or alkenyl succinates, prepared as outlined above, may
be converted to imido-acids by reaction with primary amino-acid,
especially .alpha.,.omega.-primary amino-acids. Species useful in
the current application may then be obtained by further reaction
with alcohol-amines, such as diethanolamine or aminoethyl
ethanolamine to yield mixed esters and amides of the succinic
imino-acid.
[0146] In a further broad aspect, where sulphur-content of the
film-forming additive is not an issue, sulfonyl and sulfinyl
species may be used. Thus, sulfanoyl dialkanoyl esters of
carboxylic or succinic acids,. alkanoyl hemi-esters or hemi-amides
may be employed. Alternatively, hydrocarbyl sulfonyl or sulfinyl
alkanols or N-aliphatic hydroxycarbyl hydroxyalkyl sulfinyl or
sulfonyl succinimides may be used.
(c) Polymeric Hydrocarbyl
[0147] As previously mentioned, in one preferred aspect the
film-forming additive of the present invention is (c) a polymeric
hydrocarbyl substituted with a hydroxy group and/or substituted
with a group comprising a nitrogen.
[0148] Preferably the polymeric hydrocarbyl is a polymer of
C.sub.2-C.sub.10 hydrocarbon monomers, such as C.sub.2-C.sub.8
monomers, C.sub.2-C.sub.6 monomers or C.sub.2-C.sub.4 monomers.
[0149] Preferably the polymeric hydrocarbyl is a polymeric
hydrocarbon.
[0150] Examples of suitable polymeric hydrocarbyls include the
olefin oligomerisation products obtained by the oligomerisation of
low molecular weight olefin streams, such as ethylene, propylene
and butylenes, including both 2-methylpropene and mixed
C.sub.4-monoolefin streams.
[0151] In one embodiment preferably the polymeric hydrocarbyl is a
primary alcohol.
[0152] Examples of suitable film-forming additives according to
this aspect are primary linear alcohols such as those prepared from
the various ethylene oligomerisation processes, for example
aluminium alkyls-based procedures.
[0153] In one embodiment preferably the polymeric hydrocarbyl is
substituted with a group comprising an amide group.
[0154] Suitable polymeric hydrocarbyls substituted with a group
comprising an amide group may be obtained from polymeric
hydrocarbyls in the following manner. The polymeric hydrocarbyls
may be aminated, whether directly, by formylation followed by
reductive amination or reaction with acrylonitrile followed by
reduction. Formamides of such amines may be employed.
Alternatively, such amines may be reacted with acetoacetamides or
N-substituted acetoacetamides to yield alkyl imino acetamides or
N-substituted alkyl imino acetamides. Further, hydroxyacetamides,
formed by reaction of primary ether amine with a hydroxycarboxylic
acid, such as glycolic acid, may be used.
(d) Aromatic Ring System
[0155] As previously mentioned, in one preferred aspect the
film-forming additive of the present invention is (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
[0156] Examples of suitable film-forming additives in this aspect
include hydroxylated polycyclic heteroaromatic species such as
8-hydroxyquinoline and polyhydric polycyclic aromatic species, such
as 2,3-dihydroxynaphthalene.
[0157] In this aspect preferably the film-forming additive is the
product of a Mannich reaction.
[0158] Mannich base detergents are formed by reaction of an
optionally alkylated or alkenylated phenol with formaldehyde or
other aldehyde and an amine. For example, the reaction product of
an alcohol-amine, a different diamine or other poly(amine)
containing at least one reactive primary or secondary amino group,
an aldehyde and an alkyl phenol.
Mixtures
[0159] As previously mentioned, in a preferred aspect, the
film-forming additive is one or more compounds selected from the
group consisting of (a) a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group; (b) the reaction product
of a C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; (c) a
polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
[0160] In a preferred embodiment the film-forming additive may
comprise more than one compound selected from the group consisting
of (a), (b), (c) and (d).
[0161] Thus, in one aspect, the film-forming additive comprises (a)
a C.sub.5C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group; and (d) an aromatic ring system substituted
with a hydroxy group and/or substituted with a group comprising an
amine and optionally substituted with a hydrocarbon group.
[0162] In another aspect, the film-forming additive comprises (b)
the reaction product of a C.sub.5-C.sub.100 hydrocarbyl substituted
with at least one carboxylic acid group or comprising at least one
carboxylic anhydride group with (i) a reactive alcohol; and/or (ii)
an amine; and/or (iii) an alcohol-amine; and/or (iv) an amino acid;
and (d) an aromatic ring system substituted with a hydroxy group
and/or substituted with a group comprising an amine and optionally
substituted with a hydrocarbon group.
[0163] In a further aspect, the film-forming additive comprises (a)
a C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group; (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; and (d)
an aromatic ring system substituted with a hydroxy group and/or
substituted with a group comprising an amine and optionally
substituted with a hydrocarbon group.
[0164] In another aspect, the film-forming additive comprises (a) a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group; (b) the reaction product of a
C.sub.5-C.sub.100 hydrocarbyl substituted with at least one
carboxylic acid group or comprising at least one carboxylic
anhydride group with (i) a reactive alcohol; and/or (ii) an amine;
and/or (iii) an alcohol-amine; and/or (iv) an amino acid; (c) a
polymeric hydrocarbyl substituted with a hydroxy group and/or
substituted with a group comprising a nitrogen; and (d) an aromatic
ring system substituted with a hydroxy group and/or substituted
with a group comprising an amine and optionally substituted with a
hydrocarbon group.
[0165] Examples of useful film-forming additive according to this
aspect of the present invention include Mannich base detergents in
combination with one or more of an acid, a hemi-ester, an ester, an
amide, an amido-ester, an imino or an imido compound. Further,
other dispersant-type molecules such as the PIB-amines or
poly(oxyalkylene) amines may be used in combination with the above
species. PIB-amines may be prepared from the same olefin sources as
described for the formation of alkenyl succinic acids. Typically,
higher molecular weight oligomers, e.g. 500 to 1500 amu no. average
molecular weight would be employed. The PIB-amine may be prepared
by chlorination and reaction with amine or poly(amine) or by
hydroformylation then reaction with amine or poly(amine).
Poly(alkylene) amines may be formed by oligomerisation of alkylene
(typically ethylene, propylene or butylene) oxides initiated by
amine or poly(amine).
Process
[0166] As previously mentioned, in one aspect, the present
invention provides a process for supplying a fuel composition to a
combustion engine wherein the process comprises (i) pumping the
fuel composition with a rotary pump to supply the fuel composition
to the combustion engine wherein the fuel composition comprises
diesel, a fuel alcohol and a film-forming additive.
[0167] In a preferred aspect the fuel composition further comprises
a co-solvent and/or one ore more surfactants.
[0168] Preferably the pump supplies the fuel composition to the
combustion engine at a rate which under normal design operating
conditions would result in cavitation of the pump if operated with
a fuel comprising diesel and the fuel alcohol in the absence of the
film-forming additive.
[0169] Normal design operating conditions are those in which the
pump is supplying fuel to the engine at rates sufficient to supply
the fuel requirement of the engine at all conditions from idle
speed, zero or near-zero load to rated speed (rev/min) at rated
power. This requirement may substantially exceed the fuel
consumption of the engine as in many designs there is a return of
fuel from the engine to the fuel tank without wishing to be bound
by theory it is believed that a pump is most likely to be subjected
to more rapid wear when the engine is operating at or near to rated
power.
[0170] Preferably the film-forming additive, the fuel and the fuel
alcohol are as herein defined.
[0171] In a preferred aspect the fuel composition further comprises
a co-solvent and/or one ore more surfactants.
[0172] In a broad aspect, the present invention provides a process
for supplying a fuel composition to a combustion engine wherein the
process comprises (i) pumping the fuel composition with a pump to
supply the fuel composition to the combustion engine wherein the
fuel composition comprises diesel, a fuel alcohol and a
film-forming additive.
[0173] In this aspect preferably the pump is a rotary pump. The
pump may, however be another pump such as an "in-line" pump.
EXAMPLES
Fuel Lubricity Characteristics
[0174] The lubricity of diesel fuel is most conveniently measured
by means of the test protocol well known to those skilled in the
art as the CEC F-06-A-96 HFRR test. Diesel fuel blends were tested
to this method, modified solely in respect of temperature of
execution. The standard procedure is executed at 60.degree. C.
Because of flash point concerns in blends containing ethanol, the
tests were carried out at 25.degree. C. Values for lubricity were
established. Some of the diesel fuel blends contained ethanol,
together with additional minor components as indicated in the data
set contained in Table 2. TABLE-US-00003 TABLE 2 Lubricity
characteristics of diesel fuels with and without alcohol Wear Scar
Diameter, Fuel tested microns ULSD 3 258 ULSD 3 + Ethanol + Octimax
339 EN 590 237 EN 590 + Ethanol + Octimax 313 Kerosene 732 Kerosene
+ Ethanol + Octimax 412 Kerosene + Ethanol 745
[0175] The minor component described as Octimax is a co-solvent
[STEVE --is Octimax available from a commercial source? Do you know
the chemical composition?] used to stabilise the blend of diesel
fuel with ethanol. Kerosene does not require the use of a
co-solvent, so it was possible to establish the effect of ethanol
on lubricity in kerosene independently of the use of the Octimax
component.
[0176] The presence of ethanol in a diesel fuel blend can be seen
to increase the wear scar diameter, although the effect is fuel
dependent.
[0177] The significance of the values of wear scar diameter (WSD)
obtained, lies in their relationship to wear observed in rotary
distributor type diesel injector pumps. It has been established
through extensive testing programmes with this type of pump that a
WSD value of less than 460 microns is required. This level of
lubricity in the HFRR test is commonly believed to prevent
accelerated wear in rotary distributor type pumps.
Wear in Rotary Distributor Pumps
[0178] The test protocol employed to establish wear patterns with
rotary distributor pumps is the CEC F-32-x-99 method. This 1000 h
duration protocol is an accelerated wear test method, which rates
components of the injector pump for wear, and as a result indicates
the probable acceptable life of the pump in service. On a scale of
1 to 10, a rating of 1 indicates a newly manufactured pump. Pumps
demonstrating a maximum wear rating of up to and including a value
of 3.5 at the end of the test, will be satisfactory in service, but
where the overall pump rating lies in the range 4-6, service life
will be reduced. A rating in this range therefore indicates a
failure in the 1000 hour pump test. A rating in the range 7-10 is
linked to actual failure of the pump during the test. Where this
occurs, the test is terminated before the completion of 1000 hours.
As is well known to those skilled in the art, failures on extreme
fuels can occur in less than 50 hours. The pump test method uses
the Bosch VE distributor type injection pump; the 1000 hours test
duration is based on field experiences.
[0179] It is surprisingly found that it is feasible to produce a
diesel fuel composition containing ethanol which demonstrates a
wear scar diameter (WSD) of less than 460 microns in the CEC
F-06-A-96 HFRR test, but which in the separate CEC F-32-x-99 test
involving a Bosch VE rotary distributor type diesel injector pump
shows unacceptable wear patterns. The reason for the apparent
discrepancy between the normally adequate lubricity level of 460
microns WSD, and the unacceptable rotary distributor pump wear
patterns which are observed with fuels containing ethanol, is
believed to lie in the phenomenon of cavitation as hereinbefore
described. Because of the propensity of fuels containing ethanol to
cause cavitation within the body of a rotary distributor type
diesel injection pump, it can be shown that a fuel meeting the
criterion of acceptable lubricity in the CEC F-06-A-96 HFRR test
(less than 460 micron WSD) fails to meet the criterion of
acceptable life in the CEC F-32-x-99 pump rig test (i.e. the rating
exceeds 3.5 after 1000 hours).
[0180] However, it is found that by addition of the following
film-forming additives according to the present invention to a
blend of diesel fuel and fuel alcohol, the problems of cavitation
within the body of the pump are overcome, allowing a rating of 3.5
or less to be achieved after 1000 hours of operation. This may
typically allow a satisfactory service life to be obtained with an
otherwise unsatisfactory blend of diesel fuel and fuel alcohol.
Test Results
Fuel blend sample number 2021943
[0181] A blend of fuel containing the following components was made
up: TABLE-US-00004 Swedish Class I diesel 369.2 litres (92.3%
vol/vol) (sample number 2021940) Ethanol 30.8 litres (7.7% vol/vol)
Cosolvent formulation 2 kg
[0182] The cosolvent formulation is needed to produce a stable
blend of ethanol in diesel fuel. The co-solvent formulation used
was AAE-05 available from O.sub.2Diesel Inc, Delaware, USA
(previously ME Technologies Inc.). It is understood to contain:
TABLE-US-00005 25 wt % Surfactant A C.sub.18 diethanolamide 25 wt %
Surfactant B C.sub.18 fatty acid ethoxylated with average of 7
ethoxy groups 50 wt % Co-solvent 50% C9 to C11 alcohol ethoxylate
with average 2.5 EO groups per alcohol
Fuel blend sample number 2030834
[0183] A further blend of fuel containing the following components
was made up: TABLE-US-00006 Swedish Class I diesel fuel 369.2
litres (92.3% vol/vol) (sample number 2030831) Ethanol 30.8 litres
(7.7% vol/vol) Cosolvent formulation 2 kg
[0184] The co-solvent formulation was as above.
Fuel blend sample number 2030835
[0185] A further blend of fuel containing the following components
was made up: TABLE-US-00007 Swedish Class I diesel fuel 369.2
litres (92.3% vol/vol) (sample number 2030831) Ethanol 30.8 litres
(7.7% vol/vol) Cosolvent formulation 2 kg Film forming additive 75
mg/l
[0186] The co-solvent formulation was as above. The film forming
additive used was: ##STR21##
[0187] wherein PIB was a polyisobutene having an average molecular
weight of 260.
[0188] Lubricity tests were carried out using the HFRR apparatus
according to the CEC-F-06-A-96 procedure, modified solely in
respect of temperature of execution. (The standard procedure is
executed at 60.degree. C. Because of flash point concerns, the
tests were carried out at 25.degree. C.). The results of the tests
are shown in Table 3. TABLE-US-00008 TABLE 3 Test fuel HFRR data
Wear Scar Diameter, microns Result at Result at Fuel tested Sample
number 60.degree. C. 25.degree. C. Swedish Class I 2021940 606 624
Swedish Class I + Ethanol + 2021943 -- 324 cosolvent Swedish Class
I 2030831 614 646 Swedish Class I + Ethanol + 2030834 -- 342
cosolvent Swedish Class I + Ethanol + 2030835 -- 321 cosolvent +
film forming additive
[0189] These data show that the basefuel is not much affected by
the alteration in test temperature. The data also show that the
film forming additive does not contribute significantly to
lubricity in these blends, since the results with and without the
film forming additive are the same within test repeatability.
[0190] The fuel blends containing ethanol were also each subjected
to a 1000 h pump test using the Bosch VE rotary distributor pump
according to the CEC F-32-X-99 method. The results of this test are
given below:
[0191] Fuel blend containing no film forming additive : sample
number 2021943: Pump rating 4
[0192] Fuel blend containing film forming additive: sample number
2030835: Pump rating 3
[0193] The fuel blend containing no film forming additive gives a
failing or unacceptable result in the 1000 h pump test. By
contrast, the fuel blend containing the film forming additive gives
a satisfactory, or pass result, in the 1000 h pump test. Both fuel
blends containing ethanol gave results in the HFRR test which would
suggest a pass or satisfactory result in the 1000 h pump test.
However, only the ethanol fuel blend containing the film forming
additive gave a satisfactory or pass result in the 1000h pump rig
test. The difference in performance between the fuel blends is
ascribed to inhibition or prevention by the film forming additive
of the effects of cavitation within the pump, which would otherwise
have increased wear rates as a result of the inclusion of ethanol
in the fuel blend.
[0194] Details of the pump ratings are given in Tables 4 and 5
below TABLE-US-00009 TABLE 4 Detailed pump rating : fuel sample
2021943 PRE TEST Ratings Camplate: Path n/a Centre n/a Claws n/a
Rollers n/a Roller bolts n/a Governor: Flyweights n/a Ring n/a
Supply Pump: Blades n/a Raceway n/a Washer (plunger) n/a Overall
rating n/a POST TEST Ratings Camplate: Path 2.5 Centre 2.5 Claws
2.0 Rollers 3.0 Roller bolts 4.0 Governor: Flyweights 2.0 Ring 2.0
Supply Pump: Blades 2.0 Raceway 2.0 Washer (plunger) 2.0 Overall
rating 4.0
[0195] TABLE-US-00010 TABLE 5 Detailed pump rating : fuel sample
2030835 PRE TEST Ratings Camplate: Path n/a Centre n/a Claws n/a
Rollers n/a Roller bolts n/a Governor: Flyweights n/a Ring n/a
Supply Pump: Blades n/a Raceway n/a Washer (plunger) n/a Overall
rating n/a POST TEST Ratings Camplate: Path 2.5 Centre 2.5 Claws
2.5 Rollers 2.5 Roller bolts 3.0 Governor: Flyweights 2.0 Ring 2.0
Supply Pump: Blades 2.0 Raceway 2.0 Washer (plunger) 2.0 Overall
rating 3.0
[0196] All publications mentioned in the above specification are
herein incorporated by reference. Various modifications and
variations of the described methods and system of the invention
will be apparent to those skilled in the art without departing from
the scope and spirit of the invention. Although the invention has
been described in connection with specific preferred embodiments,
it should be understood that the invention as claimed should not be
unduly limited to such specific embodiments. Indeed, various
modifications of the described modes for carrying out the invention
which are obvious to those skilled in chemistry or related fields
are intended to be within the scope of the following claims.
* * * * *
References