U.S. patent application number 13/875661 was filed with the patent office on 2013-09-19 for diesel fuel and a method of operating a diesel engine.
This patent application is currently assigned to SHELL OIL COMPANY. The applicant listed for this patent is SHELL OIL COMPANY. Invention is credited to Ralph Anthony CHERRILLO, Richard Hugh CLARK, Mary Ann DAHLSTROM, Ian Geoffrey VIRRELS.
Application Number | 20130240404 13/875661 |
Document ID | / |
Family ID | 37496739 |
Filed Date | 2013-09-19 |
United States Patent
Application |
20130240404 |
Kind Code |
A1 |
CHERRILLO; Ralph Anthony ;
et al. |
September 19, 2013 |
DIESEL FUEL AND A METHOD OF OPERATING A DIESEL ENGINE
Abstract
A diesel fuel based on a blend of a diesel fuel derived from a
Fischer-Tropsch process, and a mineral oil based diesel fuel having
a sulfur content of less than 100 ppmw; and a method of operating a
diesel engine, which method involves combusting such diesel fuel in
the diesel engine.
Inventors: |
CHERRILLO; Ralph Anthony;
(Houston, TX) ; CLARK; Richard Hugh; (Ince,
GB) ; DAHLSTROM; Mary Ann; (Katy, TX) ;
VIRRELS; Ian Geoffrey; (Ince, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHELL OIL COMPANY |
Houston |
TX |
US |
|
|
Assignee: |
SHELL OIL COMPANY
Houston
TX
|
Family ID: |
37496739 |
Appl. No.: |
13/875661 |
Filed: |
May 2, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11465642 |
Aug 18, 2006 |
8475647 |
|
|
13875661 |
|
|
|
|
60710321 |
Aug 22, 2005 |
|
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Current U.S.
Class: |
208/15 |
Current CPC
Class: |
C10G 2400/04 20130101;
C10G 2300/405 20130101; C10G 2300/1022 20130101; C10G 2300/202
20130101; C10G 2/32 20130101; C10L 1/08 20130101; C10G 2/00
20130101; C10G 2300/1055 20130101; C10G 2300/80 20130101; C10L
1/1616 20130101 |
Class at
Publication: |
208/15 |
International
Class: |
C10L 1/16 20060101
C10L001/16 |
Claims
1. A diesel fuel blend that provides a relative reduction to the
emission of oxides of nitrogen when combusted in a heavy duty
diesel engine, the diesel fuel blend comprising: (a) a diesel fuel
derived from a Fischer-Tropsch process; and (b) a mineral oil based
diesel fuel having a sulfur content of less than 100 ppmw; wherein
the weight fraction of component (a) in the blend is between 0.28
and 0.5.
2. The diesel fuel blend as defined in claim 1 wherein the weight
fraction of component (a) in the blend is between 0.28 and 0.4.
3. The diesel fuel blend as defined in claim 1 wherein the weight
fraction of component (a) in the blend is between 0.3 and 0.35.
4. The diesel fuel blend as defined in claim 1 wherein the diesel
fuel further comprises one or more additives selected from the
group consisting of detergents, dehazers, anti-foaming agents,
anti-rust agents, anti-static agents, pipeline drag reducers, flow
improvers, lubricity additives, antioxidants and wax anti-settling
agents.
5. The diesel fuel blend as defined in claim 1 wherein the diesel
fuel further comprises a lubricity additive.
6. The diesel fuel blend as defined in claim 1 wherein, when
combusted, said diesel fuel produces an emission of oxides of
nitrogen from said combustion which is P % lower than an emission
of oxides of nitrogen which can be calculated on the basis of a
linear blending behavior of components (i) and (ii), P is relative
to the emission of oxides of nitrogen caused by the said mineral
oil based diesel fuel, and P is defined by the equation P=AX(1-X),
in which equation A is a number in the range of from 10 to 25, and
X is the weight fraction of component (i) in the blend, expressed
as a number in the range of from 0 to 1.
7. The diesel fuel blend as defined in claim 1 wherein upon
combustion, said fuel blend produces an emission of oxides of
nitrogen that is lower than an emission of oxides of nitrogen that
can be calculated on the basis of linear blending behavior of
components (a) and (b).
8. A diesel fuel blend providing a relative reduction to the
emission of oxides of nitrogen when combusted in a heavy duty
diesel engine, the diesel fuel blend comprising: (a) a diesel fuel
derived from a Fischer-Tropsch process; and (b) a mineral oil based
diesel fuel having a sulfur content of less than 100 ppmw and a
T.sub.90 of more than 261.degree. C., wherein the weight fraction
of component (a) in the blend is between 0.28 and 0.5.
9. The diesel fuel blend as defined in claim 8 wherein the mineral
oil based diesel fuel has a T.sub.90 of more than 275.degree.
C.
10. The diesel fuel blend as defined in claim 8 wherein the mineral
oil based diesel fuel has a T.sub.90 of more than 285.degree.
C.
11. The diesel fuel blend as defined in claim 8 wherein the diesel
fuel further comprises one or more additives selected from the
group consisting of detergents, dehazers, anti-foaming agents,
anti-rust agents, anti-static agents, pipeline drag reducers, flow
improvers, lubricity additives, antioxidants and wax anti-settling
agents.
12. The diesel blend fuel as defined in claim 8 wherein the diesel
fuel further comprises a lubricity additive.
13. The diesel blend fuel of claim 8 wherein the diesel fuel
derived from a Fischer-Tropsch process, component (a), exhibits: a
boiling range of from about 150.degree. C. to 400.degree. C.; a T90
of from 280.degree. C. to 340.degree. C.; a density of from 0.76
g/mL to 0.79 g/mL at 15.degree. C; a cetane number of at least 60;
and a viscosity of from 2.5 centistokes to 4 centistokes at
40.degree. C.
14. The diesel fuel of claim 8 wherein the mineral oil based diesel
fuel, component (b), exhibits: a boiling range of from 158.degree.
C. to 355.degree. C.; a polynuclear aromatics (PNA) content of at
most 20%; a cetane number of at least 25; a Ramsbottom on 10% of at
most 0.15; a nitrogen content of at mot 100 ppmw; and a cyclic
paraffin content of at least 5% by weight.
15. The diesel fuel of claim 14 wherein the mineral oil based
diesel fuel, component (b), exhibits: a boiling range of from
158.degree. C. to 355.degree. C.; a polynuclear aromatics (PNA)
content of at most 20%; a cetane number of at least 25; a
Ramsbottom on 10% of at most 0.15; a nitrogen content of at mot 100
ppmw; and a cyclic paraffin content of at least 5% by weight.
16. The diesel fuel blend as defined in claim 8 wherein, when
combusted, said diesel fuel produces an emission of oxides of
nitrogen from said combustion which is P % lower than an emission
of oxides of nitrogen which can be calculated on the basis of a
linear blending behavior of components (i) and (ii), P is relative
to the emission of oxides of nitrogen caused by the said mineral
oil based diesel fuel, and P is defined by the equation P=AX(1-X)
in which equation A is a number in the range of from 10 to 25, and
X is the weight fraction of component (i) in the blend, expressed
as a number in the range of from 0 to 1.
17. The diesel fuel blend as defined in claim 8 wherein upon
combustion, said fuel blend produces an emission of oxides of
nitrogen that is lower than an emission of oxides of nitrogen that
can be calculated on the basis of linear blending behavior of
components (a) and (b).
18. The diesel fuel blend of claim 8 wherein the blend has a
boiling range of from 160.degree. C. to 355.degree. C.; a T.sub.90
of at least 310.degree. C.; an aromatic content less than or equal
to 20% w; a cetane number of at least 42; a sulfur content of less
than 50 ppm; a Ramsbottom on 10% of less than 0.15; and a nitrogen
content of less than 10 ppm.
19. The diesel fuel blend of claim 8 wherein the diesel fuel
derived from the Fischer-Tropsch process, component (a) comprises:
at least 90% w of iso and linear paraffins; a boiling range of from
about 150.degree. C. to 400.degree. C.; a T.sub.90 of from
280.degree. C. to 340.degree. C.; a density of from 0.76 g/mL
to0.79 g/mL at 15.degree. C.; a cetane number of at least 60; and a
viscosity of from 2.5 centistokes to 4 centistokes at 40.degree.
C.
20. A diesel fuel blend that provides a relative reduction to the
emission of oxides of nitrogen when combusted in a heavy duty
diesel engine, the diesel fuel blend comprising: (a) a diesel fuel
derived from a Fischer-Tropsch process, diesel fuel derived from
the Fischer-Tropsch process comprising at least 90% w of iso and
linear paraffins, a boiling range of from about 150.degree. C. to
400.degree. C., a T.sub.90 of from 280.degree. C. to 340.degree.
C., a density of from 0.76 g/mL to0.79 g/mL at 15.degree. C., a
cetane number of at least 60, and a viscosity of from 2.5
centistokes to 4 centistokes at 40.degree. C.; and (b) a mineral
oil based diesel fuel having a sulfur content of less than 100
ppmw; wherein the weight fraction of component (a) in the blend is
between 0.28 and 0.5; and wherein, when combusted, said diesel fuel
blend produces an emission of oxides of nitrogen from said
combustion which is P % lower than an emission of oxides of
nitrogen which can be calculated on the basis of a linear blending
behavior of components (i) and (ii), P is relative to the emission
of oxides of nitrogen caused by the said mineral oil based diesel
fuel, and P is defined by the equation P=AX(1-X), in which equation
A is a number in the range of from 10 to 25, and X is the weight
fraction of component (i) in the blend, expressed as a number in
the range of from 0 to 1.
Description
RELATED APPLICATIONS
[0001] This application is a divisional application of U.S. patent
application Ser. No. 11/465,642, filed Aug. 18, 2006, now issued as
U.S. Pat. No. ______; which claims the benefit of U.S. Provisional
application 60/710,321, filed Aug. 22, 2005.
FIELD OF THE INVENTION
[0002] The invention relates to a diesel fuel comprising a diesel
fuel derived from a Fischer-Tropsch process, and a mineral oil
based diesel fuel. The invention also relates to a method of
operating a diesel engine, which method comprises combusting such
diesel fuel in the diesel engine.
BACKGROUND OF THE INVENTION
[0003] Diesel engine manufacturers and diesel fuel producers are
continuously challenged to meet lower emission standards set forth
by the U.S. Environmental Protection Agency (EPA), as well as other
such agencies worldwide. These standards for both diesel and
gasoline engines mandate limits for unburned hydrocarbons, carbon
monoxide and oxides of nitrogen.
[0004] The toxicity of oxides of nitrogen and their ability to
further react to produce additional toxic materials make them an
undesirable by-product from the burning of hydrocarbons. When
released into the atmosphere, these compounds and their products
comprise what is commonly referred to as "smog", a brownish haze
seen over most major metropolitan areas.
[0005] The Engineering Society for Advancing Mobility Land Sea Air
and Space mentioned in a paper that it appears that where a
conventional diesel fuel is blended with a diesel fuel derived from
a Fisher-Tropsch process, reductions in concentrations of emissions
are generally reduced in a proportional fashion by adding
increasing amounts of the Fischer-Tropsch fuel. In particular,
emissions of oxides of nitrogen appear to follow this trend. (see
SAE Technical Paper 2000-01-1912, page 6).
[0006] It would be useful to improve the methods by which
reductions in emissions of oxides of nitrogen can be
accomplished.
SUMMARY OF THE INVENTION
[0007] The invention provides a diesel fuel comprising a blend
consisting essentially of [0008] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0009] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw.
[0010] The invention also provides a method of operating a diesel
engine, which method comprises combusting in the diesel engine a
diesel fuel comprising a blend consisting essentially of [0011] (a)
a diesel fuel derived from a Fischer-Tropsch process; and [0012]
(b) a mineral oil based diesel fuel having a sulfur content of less
than 100 ppmw.
[0013] In an embodiment, the invention provides a diesel fuel
comprising a blend consisting essentially of [0014] (a) a diesel
fuel derived from a Fischer-Tropsch process; and [0015] (b) a
mineral oil based diesel fuel having a sulfur content of less than
100 ppmw; [0016] wherein the weight fraction of component (a) in
the blend is between 0.2 and 0.5.
[0017] In another embodiment, the invention provides a method of
operating a diesel engine, which method comprises combusting in the
diesel engine a diesel fuel comprising a blend consisting
essentially of [0018] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0019] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw; [0020] wherein
the weight fraction of component (a) in the blend is between 0.2
and 0.5.
[0021] In another embodiment, the invention provides a diesel fuel
comprising a blend consisting essentially of [0022] (a) a diesel
fuel derived from a Fischer-Tropsch process; and [0023] (b) a
mineral oil based diesel fuel having a sulfur content of less than
100 ppmw and a T.sub.90 of more than 261.degree. C.
[0024] In another embodiment, the invention provides a method of
operating a diesel engine, which method comprises combusting in the
diesel engine a diesel fuel comprising a blend consisting
essentially of [0025] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0026] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw and a T.sub.90
of more than 261.degree. C.
[0027] In another embodiment, the invention provides a method of
operating a heavy duty diesel engine, which method comprises
combusting in the diesel engine a diesel fuel comprising a blend
consisting essentially of [0028] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0029] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw.
[0030] In another embodiment, the invention provides a method of
operating a diesel engine, which method comprises combusting in the
diesel engine a diesel fuel comprising a blend consisting
essentially of [0031] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0032] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw, [0033] wherein
the diesel engine produces an emission of oxides of nitrogen which
is P % lower than an emission of oxides of nitrogen which can be
calculated on the basis of a linear blending behavior of components
(a) and (b), P is relative to the emission of oxides of nitrogen
caused by the said mineral oil based diesel fuel, and P is defined
by the equation
[0033] P=AX(1-X),
in which equation A is a number in the range of from 10 to 25, and
X is the weight fraction of component (a) in the blend, expressed
as a number in the range of from 0 to 1.
[0034] In another embodiment, the invention provides a method of
reducing the emission of oxides of nitrogen caused by diesel engine
powered vehicles participating in traffic, which method comprises
[0035] providing a diesel fuel comprising a blend consisting
essentially of [0036] (a) a diesel fuel derived from a
Fischer-Tropsch process; and [0037] (b) a mineral oil based diesel
fuel having a sulfur content of less than 100 ppmw, [0038] wherein
the weight fraction of component (a) in the blend is between 0.2
and 0.5, and combusting the diesel fuel in the diesel engines of at
least 50 vehicles of the vehicles participating in said
traffic.
BRIEF DESCRIPTION OF THE DRAWING
[0039] FIG. 1 shows a plot of emissions of oxides of nitrogen ("y")
found when testing a Fuel A, a Fuel B, and blends of Fuels A and B,
as detailed in the Examples hereinafter. "x" represents the weight
fraction of Fuel B in the blends, expressed in % w. The value of
the emission found for Fuel A is normalized to 100 (i.e. y=100 when
x=0).
DETAILED DESCRIPTION OF THE INVENTION
[0040] When a diesel fuel comprising a blend of a mineral oil based
diesel fuel having a low sulfur content and a diesel fuel derived
from a Fischer-Tropsch process is combusted in a diesel engine in
accordance with this invention, a significant reduction in the
emission of oxides of nitrogen is accomplished.
[0041] Unexpectedly, the emission of oxides of nitrogen appears to
be non-linear with the blend composition. It is advantageous that
the non-linear blending behavior is such that the blends provide
lower emissions of oxides of nitrogen relative to the emissions
which can be calculated on the assumption of a linear blending
behavior. An important aspect of this invention is that this allows
for blends having a relatively low weight fraction of the
Fischer-Tropsch derived diesel fuel to provide for a relatively low
emission of oxides of nitrogen.
[0042] Another important aspect of this invention is the insight
that, on the basis of a certain quantity of Fischer-Tropsch derived
diesel fuel, a greater reduction in the cumulative emission of
oxides of nitrogen caused by a large numbers of diesel engine
powered vehicles participating in traffic can be achieved by
combusting in the diesel engines of such vehicles the
Fischer-Tropsch derived diesel fuel in the form of a blend with the
mineral oil based diesel fuel, as opposed to combusting the
Fischer-Tropsch derived diesel fuel separately from the mineral oil
based diesel fuel. The greatest reduction in the cumulative
emission can be achieved by employing a blend having a relatively
low weight fraction of the Fischer-Tropsch derived diesel fuel, for
example blends wherein said weight fraction is between 0.2 and
0.5.
[0043] Also, in accordance with this invention, blends of a diesel
fuel derived from the Fischer-Tropsch process and the mineral oil
based diesel fuel have an advantageously low value of the
Ramsbotton on 10%. The value is better than may be expected when
assuming a linear blending behavior for such diesel fuels with
respect to the value of the Ramsbotton on 10%. This indicates that
the blends have an advantageous behavior in a tendency to produce
less coke.
[0044] The diesel engine may be any combustion engine suitable for
combusting diesel fuel and may be operated in any suitable fashion
for combusting diesel fuel. Generally, the diesel engine may be a
heavy-duty diesel engine or a light duty diesel engine. As used
herein, a heavy-duty diesel engine has a volume of displacement
greater than 8.3 L, and a light-duty engine has a volume of
displacement of 8.3 L or less. Preferably, the diesel engine is a
heavy-duty engine, for example as used in construction machines,
tractor-trailers and buses. However, a light-duty diesel engine,
for example, as used in pickups, sport utility vehicles, Class 3
delivery trucks, vans, taxis and passenger cars, may be used as
well.
[0045] For purposes of this specification, various properties are
as measured as follows: density in g/mL by ASTM Method D4052,
sulfur content in ppmw by ASTM Method D4053, nitrogen content in
ppmw by ASTM Method D4629, boiling points and boiling point ranges
(in .degree. C.) by ASTM Method D0086, aromatics content in % w by
ASTM Method D5186, polynuclear aromatics (PNA) content in % w by
ASTM Method D5186, cetane number by ASTM Method D0613, linear, iso-
and cyclo-paraffins contents in % w by ASTM Method D2425, and
Ramsbottom on 10% by ASTM D524. As used herein, "ppmw" means parts
per million by weight, and "% w" means percent by weight. In
addition, by T.sub.90 is meant the distillation temperature at
which 90% of the fuel has been evaporated.
[0046] A useful method for determining emissions of oxides of
nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, and
particulate matter (all in g/hp-hr) is detailed in the EPA Federal
Test Procedure in the Code of Federal Regulations, Title 40, Part
86, Subpart N (40 CFR .sctn.86(N)). Emission measurements on the
basis of the method detailed therein, and used in the Examples
hereinafter, may provide a suitable yardstick for the reduction of
emissions of oxides of nitrogen which can be achieved when
practicing this invention.
[0047] In the practice of this invention a diesel fuel is employed
which comprises a blend consisting of a diesel fuel derived from a
Fischer-Tropsch process ("component (a)") and a mineral oil based
diesel fuel ("component (b)"). Component (b) has a sulfur content
of less than 100 ppmw.
[0048] The weight fraction of component (a) in the blend may vary
between wide ranges. Typically, the weight fraction of component
(a) is more than 0.2, more typically at least 0.25, preferably at
least 0.28, and more preferably at least 0.3. Typically, the weight
fraction of component (a) is less than 0.5, more typically at most
0.4, and preferably at most 0.35. The component (b) represents the
balance in the blend.
[0049] Component (a), the Fischer-Tropsch derived diesel fuel, may
be any diesel fuel which is prepared from the product of a
Fischer-Tropsch process. The diesel fuel product may be obtained by
fractionation of such a Fischer-Tropsch process product or obtained
from a hydroconverted (via hydrocracking/hydroisomerization)
Fischer-Tropsch process product. Examples of Fischer-Tropsch
derived diesel fuels are described in EP-A-583836, WO-A-9714768,
WO-A-9714769, WO-A-011116, WO-A-011117, WO-A-0183406, WO-A-0183648,
WO-A-0183647, WO-A-0183641, WO-A-0020535, WO-A-0020534,
EP-A-1101813 and U.S. Pat. No. 6,204,426, all of which are hereby
incorporated by reference. The Fischer-Tropsch process is a well
known method for producing hydrocarbons, see for example, U.S. Pat.
No. 4,686,238; U.S. Pat. No. 5,037,856; U.S. Pat. No. 5,958,985;
U.S. Pat. No. 6,759,440; U.S. Pat. No. 6,806,297; and U.S. Pat. No.
6,852,762, all of which are herein incorporated by reference.
[0050] Suitably, component (a), the Fischer-Tropsch derived diesel
fuel, may comprise at least 90% w, more preferably at least 95% w,
of iso and linear paraffins, for example up to at most 99.9% w. The
weight ratio of iso-paraffins to normal paraffins may suitably be
greater than 0.3. This ratio may be up to 12. Suitably this ratio
is between 2 and 6. The actual value for this ratio may be
determined, in part, by the hydroconversion process used to prepare
the Fischer-Tropsch derived diesel fuel from the Fischer-Tropsch
synthesis product. Cyclic-paraffins may be present, but this amount
is typically below 5% w, and frequently at least 0.1% w. By virtue
of the Fischer-Tropsch process, component (a) has essentially zero
content of sulfur and nitrogen (or amounts which are no longer
detectable). The content of sulfur may typically be less than 1
ppmw. The content of nitrogen may typically be less than 1 ppmw.
These hetero-atom compounds are poisons for Fischer-Tropsch
catalysts and are typically removed from the synthesis gas that is
the feed for the Fischer-Tropsch process. Typically, the process
does not make aromatics, or as usually operated, virtually no
aromatics are produced. The content of aromatics may typically be
below 2% w, more typically at most 1% w, preferably at most 0.5% w,
and frequently at least 0.01% w. The content of polynuclear
aromatics (PNA) may typically be below 1% w, preferably at most
0.5% w, and frequently at least 0.005% w.
[0051] Component (a), the Fischer-Tropsch derived diesel fuel, may
suitably have a boiling range which may be from about 150.degree.
C. to 400.degree. C. Component (a) may suitably have a T.sub.90 of
from 280.degree. C. to 340.degree. C. The density of component (a)
may be in the range of from 0.76 g/mL to 0.79 g/mL at 15.degree. C.
The cetane number of component (a) may be at least 60, preferably
at least 70, more preferably at least 74. Frequently, the cetane
number of component (a) may be at most 90, more frequently at most
85, in particular at most 80. The viscosity of component (a) may be
in the range of from 2.5 centistokes to 4 centistokes at 40.degree.
C.
[0052] The diesel fuel of component (b) may be prepared from any
mineral oil. The mineral oil based diesel fuel of component (b) may
suitably have a boiling range of from 158.degree. C. to 355.degree.
C. The T.sub.90 boiling point may suitably be more than 261.degree.
C., more suitably at least 265.degree. C., preferably at least
275.degree. C. and more preferably at least 285.degree. C. The
T.sub.90 may preferably be at most 330.degree. C. and more
preferably at most 325.degree. C. The aromatics content may
suitably be less than 30% w, preferably at most 20% w and most
preferably at most 10% w. The aromatics content may typically be at
least 2% w, more typically at least 5% w. The polynuclear aromatics
(PNA) content may preferably be at most 20% w, more preferably at
most 15% w, most preferably at most 5% w. The polynuclear aromatics
(PNA) content may typically be at least 1% w, more typically at
least 1.5% w. The cetane number may suitably be at least 25, more
suitably at least 35 and preferably at least 40. The cetane number
may suitably be at most 55, more suitably at most 50 and preferably
at most 45. The sulfur content may preferably be at most 50 ppmw,
more preferably at most 10 ppmw, and most preferably at most 5
ppmw. The sulfur content may typically be at least 1 ppmw, more
typically at least 1.5 ppmw. The Ramsbottom on 10% may suitably be
at most 0.15, preferably at most 0.10 and more preferably at most
0.07. In the normal practice of this invention, the Ramsbottom on
10% may frequently be at least 0.01, or more frequently at least
0.02. The nitrogen content of component (b) may suitably be at most
100 ppmw, preferably at most 50 ppmw, more preferably at most 25
ppmw. The nitrogen content may frequently be at least 1 ppmw, more
frequently at least 2 ppmw. The cyclic-paraffins content may be at
least 5% w and typically at most 10% w.
[0053] The blend of components (a) and (b) may suitably have a
boiling range of from 160.degree. C. to 355.degree. C. Suitably,
the T.sub.90 may be at least 310.degree. C., preferably at least
315.degree. C. and more preferably at least 320.degree. C. The
T.sub.90 may suitably be at most 340.degree. C., preferably at most
335.degree. C. and more preferably at most 330.degree. C. The
aromatics content may suitably be less than or equal to 30% w,
preferably at most 15% w and most preferably at most 10% w. In the
normal practice of this invention, the aromatics content may
frequently be at least 0.5% w, more frequently at least 1% w. The
cetane number may typically be at least 42, preferably at least 45
and more preferably, the cetane number may be at least 50. The
cetane number may typically be at most 68, more typically at most
65, preferably at most 60 and more preferably, at most 55. The
sulfur content may preferably be less than 50 ppm, more preferably
less than 10 ppm, and most preferably less than 5 ppm. Frequently
the sulfur content is at least 0.1 ppmw, more frequently at least
0.2 ppmw. The Ramsbottom on 10% may suitably be less than 0.15,
preferably less than 0.10 and more preferably less than 0.07. The
nitrogen content of the blend may suitably be less than 10 ppm,
preferably less than 8 ppm, more preferably less than 6 ppm.
Frequently, the nitrogen content is at least 0.1 ppmw, more
frequently at least 1 ppmw.
[0054] The diesel fuels may be additized (additive-containing)
fuels or unadditized (additive-free) fuels. If additized, the fuels
may contain minor amounts of one or more additives selected, for
example, from anti-static agents, pipeline drag reducers, flow
improvers (e.g. ethylene/vinyl acetate copolymers or
acrylate/maleic anhydride copolymers), lubricity additives,
antioxidants and wax anti-settling agents. Typically, the blend of
components (a) and (b) may constitute at least 90% w of the diesel
fuel of this invention, or for use in this invention. More
typically, the blend of components (a) and (b) may constitute at
least 95% w of the diesel fuel, or even more, such as for example
98% w or 99% w. Typically, the blend of components (a) and (b) may
constitute at most 100% w of the diesel fuel, more typically at
most 99.9% or at most 99.5% w.
[0055] Detergent-containing diesel fuel additives are known and
commercially available. Such additives may be added to the diesel
fuel at levels intended to reduce, remove, or slow the build up of
engine deposits.
[0056] Examples of detergents suitable for use as an additive for
the present purpose fuel include polyolefin substituted
succinimides or succinamides of polyamines, for instance
polyisobutylene succinimides or polyisobutylene amine succinamides,
aliphatic amines, Mannich bases or amines and polyolefin (e.g.
polyisobutylene) maleic anhydrides. Succinimide dispersant
additives are described for example in GB-A-960493, EP-A-0147240,
EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808.
Particularly preferred are polyolefin substituted succinimides such
as polyisobutylene succinimides.
[0057] The additive may contain other components in addition to the
detergent. Examples are lubricity enhancers; dehazers, e.g.
alkoxylated phenol formaldehyde polymers; anti-foaming agents (e.g.
polyether-modified polysiloxanes); ignition improvers (cetane
improvers) (e.g. 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate,
di-tert-butyl peroxide and those disclosed in U.S. Pat. No.
4,208,190 at column 2, line 27 to column 3, line 21); anti-rust
agents (e.g. a propane-1,2-diol semi-ester of tetrapropenyl
succinic acid, or polyhydric alcohol esters of a succinic acid
derivative, the succinic acid derivative having on at least one of
its alpha-carbon atoms an unsubstituted or substituted aliphatic
hydrocarbon group containing from 20 to 500 carbon atoms, e.g. the
pentaerythritol diester of polyisobutylene-substituted succinic
acid); corrosion inhibitors; reodorants; anti-wear additives;
anti-oxidants (e.g. phenolics such as 2,6-di-tert-butylphenol, or
phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine);
metal deactivators; and combustion improvers.
[0058] It is particularly preferred that the additive include a
lubricity enhancer, especially as the diesel fuel composition has a
low sulfur content. In the additized fuel composition, the
lubricity enhancer is conveniently present at a concentration of at
most 1000 ppmw, preferably between 50 and 1000 ppmw, more
preferably between 100 and 1000 ppmw. Suitable commercially
available lubricity enhancers include ester- and acid-based
additives. Other lubricity enhancers are described in open
literature references, in particular in connection with their use
in low sulfur content diesel fuels, for example in: the paper by
Danping Wei and H. A. Spikes, "The Lubricity of Diesel Fuels",
Wear, III (1986) 217-235; WO-A-95/33805 (describing cold flow
improvers to enhance lubricity of low sulfur fuels); WO-A-94/17160
(describing certain esters of a carboxylic acid and an alcohol
wherein the acid has from 2 to 50 carbon atoms and the alcohol has
1 or more carbon atoms, particularly glycerol monooleate and
di-isodecyl adipate, as fuel additives for wear reduction in a
diesel engine injection system); U.S. Pat. No. 5,490,864
(describing certain dithiophosphoric diester-dialcohols as
anti-wear lubricity additives for low sulfur diesel fuels; and
WO-A-98/01516 (describing certain alkyl aromatic compounds having
at least one carboxyl group attached to their aromatic nuclei, to
confer anti-wear lubricity effects particularly in low sulfur
diesel fuels); which references are all incorporated herein by
reference.
[0059] It is also preferred that the additive contain an
anti-foaming agent, more preferably in combination with an
anti-rust agent and/or a corrosion inhibitor and/or a lubricity
additive.
[0060] Unless otherwise stated, the (active matter) concentration
of each such additional component in the additized fuel composition
is preferably up to 10000 ppmw, more preferably in the range from
0.1 to 1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from
0.1 to 150 ppmw, relative to the weight of the diesel fuel.
[0061] The (active matter) concentration of any dehazer in the fuel
composition may preferably be in the range from 0.1 to 20 ppmw,
more preferably from 1 to 15 ppmw, still more preferably from 1 to
10 ppmw, advantageously from 1 to 5 ppmw, relative to the weight of
the diesel fuel. The (active matter) concentration of any ignition
improver present may preferably be 2600 ppmw or less, more
preferably 2000 ppmw or less, conveniently from 300 to 1500 ppmw,
relative to the weight of the diesel fuel.
[0062] The additive may typically contain a detergent, optionally
together with other components as described above, and a diesel
fuel-compatible diluent, which may be a carrier oil (e.g. a mineral
oil), a polyether, which may be capped or uncapped, a non-polar
solvent such as toluene, xylene, white spirits and those sold by
Shell companies under the trade mark "SHELLSOL", and/or a polar
solvent such as an ester and, in particular, an alcohol, e.g.
hexanol, 2-ethylhexanol, decanol, isotridecanol and alcohol
mixtures such as those sold by Shell companies under the trade mark
"LINEVOL", especially LINEVOL 79 alcohol which is a mixture of
C.sub.7-9 primary alcohols, or a C.sub.12-14 alcohol mixture which
is commercially available.
[0063] If desired, the additive components, as listed above, may be
co-mixed, preferably together with suitable diluent(s), in an
additive concentrate, and the additive concentrate may be dispersed
into the fuel, in suitable quantity to result in a composition of
the present invention. The blend of components (a) and (b) may be
prepared by blending the component (a) with component (b).
[0064] As indicated hereinbefore, significant reductions in
emissions of oxides of nitrogen are found when, in accordance with
this invention, a diesel fuel comprising a blend consisting of the
diesel fuel derived from a Fischer-Tropsch process and the mineral
oil based diesel fuel having a sulfur content of less than 100 ppmw
is combusted in a diesel engine. The reduction is relative to the
emission which is found when combusting a diesel fuel comprising
the said mineral oil based diesel fuel, without the diesel fuel
derived from a Fischer-Tropsch process, and may typically amount to
at least 5%, more typically at least 7%, and typically at most 25%,
more typically at most 20%.
[0065] It has also been indicated hereinbefore that with respect to
the emission of oxides of nitrogen the diesel fuel derived from a
Fischer-Tropsch process and the mineral oil based diesel fuel
having a sulfur content of less than 100 ppmw exhibit a non-linear
blending behavior, which unexpectedly provides a larger decrease in
the emission of oxides of nitrogen than would be expected on the
basis of a linear blending behavior. When combusting in the diesel
engine the diesel fuel comprising the blend consisting of the
diesel fuel derived from a Fischer-Tropsch process and the mineral
oil based diesel fuel having a sulfur content of less than 100
ppmw, the diesel engine unexpectedly produces an emission of oxides
of nitrogen which is P % lower than an emission of oxides of
nitrogen which can be calculated on the assumption of a linear
blending behavior of the two components in the blend, P is relative
to the emission of oxides of nitrogen caused by the said mineral
oil based diesel fuel, and P is defined by the equation
P=AX(1-X),
in which equation A is a number in the range of from 10 to 25, and
X is the weight fraction of the diesel fuel derived from a
Fischer-Tropsch process in the blend, expressed as a number in the
range of from 0 to 1.
[0066] The value of A may typically be at least 12, more typically
at least 14. The value of A may typically be at most 20, more
typically at most 18. The value of A may be for example 16.
[0067] An important aspect of the invention is that the
advantageous non-linear blending behaviour enables a more efficient
use of diesel fuel derived from a Fischer-Tropsch process when
combating emissions of oxides of nitrogen caused by diesel engine
powered vehicles participating in traffic. Such traffic may be the
traffic of a country, or it may be the local traffic in a city or
in a smaller community, such as a town or village. The number of
vehicles involved may amount to for example at least 50 or at least
100, preferably at least 1000 and more preferably greater than
10,000. The vehicles may or may not be the vehicles of a fleet. The
vehicles of a fleet are understood to be those vehicles that are
commonly owned or controlled. Preferably, the fleet may comprise at
least 50 vehicles, typically at least 100 vehicles, more typically
at least 500, and preferably at least 1000 vehicles. Vehicles
belonging to the fleet may be, for example, busses,
tractor-trailers, or taxis. As indicated hereinbefore, on the basis
of a certain quantity of a diesel fuel derived from a
Fischer-Tropsch process a larger decrease in the cumulative
emissions of oxides of nitrogen can be achieved when diesel engine
powered vehicles participating in said traffic are fuelled with
diesel fuel comprising a blend in accordance with this invention
rather than with a diesel fuel comprising the diesel fuel derived
from a Fischer-Tropsch process without the mineral oil based diesel
fuel.
[0068] The examples below are intended to further illustrate the
invention and are not to be construed as limiting the scope
thereof.
EXAMPLES
[0069] Experiments comprised testing a Fischer-Tropsch derived
diesel fuel (Fuel B) alone, a mineral oil based diesel fuel (Fuel
A) and blends of Fuel A and Fuel B. The properties and
corresponding ASTM method of analysis of the fuels and one of the
blends used in these examples are given in Table I.
TABLE-US-00001 TABLE I Blend of 45% w Method Fuel Fuel Fuel A and
Property (ASTM) A B 55% w Fuel B Density (g/mL) D4052 0.8314 0.7865
0.8067 Sulfur (ppmw) D4053 1.6 0.3 1.0 Nitrogen (ppmw) D4629 5.7
<1.0 3.0 T.sub.10 (.degree. C.) D0086 181 246 192 T.sub.50
(.degree. C.) D0086 298 298 272 T.sub.90 (.degree. C.) D0086 331
331 330 Aromatics (% w) D5186 9.2 0.5 4.5 PNA (% w) D5186 2.5 0.1
0.8 Cetane Number D0613 42.7 >76 65 Ramsbotton on D524 0.07 0.03
0.04 10%
[0070] The testing protocol for the examples was the California Air
Resources Board (CARB) Procedure for Certification of Emissions
Reductions for Alternative Fuels--Alternative 3. The diesel engine
operated was a 1991 Detroit Diesel Corporation (DDC) Series 60 HDD
engine, a heavy duty engine, installed in a transient capable test
cell. The testing involved seven days of three consecutive hot
starts per day with a 20 minute engine-off soak between runs on
each fuel. Emissions of the following were measured according to
the EPA Federal Test Procedure in the Code of Federal Regulations,
Title 40, Part 86, Subpart N (40 CFR .sctn.86(N)): hydrocarbons
(HC), carbon monoxide (CO), carbon dioxide (CO.sub.2), oxides of
nitrogen (NO.sub.x) and particulate matter (PM). Results are given
in Table II.
TABLE-US-00002 TABLE II HC CO CO.sub.2 NO.sub.x PM Fuel A Fuel B
(g/ (g/ (g/ (g/ (g/ (% w) (% w) hp-hr) hp-hr) hp-hr) hp-hr) hp-hr)
100 .sup. 0.sup. 0.112 2.21 552.4 4.906 0.146 80 *) 20 *) 0.093
2.08 547.7 4.542 0.158 67 *) 33 *) 0.082 2.00 545.5 4.421 0.154 45
*) 55 *) 0.066 1.84 545.1 4.254 0.148 25 *) 75 *) 0.055 1.76 541.5
4.046 0.139 0.sup. 100 .sup. 0.041 1.62 532.9 4.007 0.127 *) in
accordance with the invention, others for comparison
[0071] Table III shows the emissions of oxides of nitrogen relative
to the emission of emission of oxides of nitrogen found in the case
of Fuel A (i.e. the mineral oil based diesel fuel; Fuel A is taken
as 100), and the reduction in the emissions relative to the
emission found in the case of Fuel A.
TABLE-US-00003 TABLE III Fuel Fuel NO.sub.x Reduction in NO.sub.x
emissions, A B emissions relative to emission caused P (% w) (% w)
(Fuel A = 100) by Fuel A (%) (%) 100 .sup. 0.sup. 100 0 0 80 *) 20
*) 92.6 7.42 3.74 67 *) 33 *) 90.1 9.89 3.86 45 *) 55 *) 86.7 13.3
3.24 25 *) 75 *) 82.5 17.5 3.78 0.sup. 100 .sup. 81.7 18.3 0 *) in
accordance with the invention, others for comparison
[0072] The Figure shows a plot of the emissions of oxides of
nitrogen relative to the emission of oxides of nitrogen found in
the case of Fuel A (i.e. the mineral oil based diesel fuel; Fuel A
is taken as 100) and a curve fitted to these data. The curve
follows the equation
y=0.0015x.sup.2-0.3322x+99.689 (1)
wherein y represents the emissions of oxides, taking 100 as the
value for Fuel A; and x represents the weight fraction of Fuel B
(the Fisher-Tropsch derived diesel fuel) in the blend, expressed in
% w. The Figure shows also a straight line representing a notional
linear blending behavior of the Fuels A and B. This straight line
follows the equation
y=-0.183x+100 (2)
wherein y and x are as defined hereinbefore. Because of the
non-linear blending behavior, there is unexpectedly and
advantageously an extra decrease in the emissions of oxides of
nitrogen.
[0073] For each of the blends, the value of the extra decrease as a
result of non-linear blending behavior has been calculated from the
values presented in the right column of Table III and values which
can be calculated from equation (2). The calculated values of the
extra decrease (P, in %, relative to the emission of oxides of
nitrogen found in the case of Fuel A) have been shown in Table III.
P appears to follow the equation
P=0.0016x(100-x), or
P=16X(1-X),
wherein x is as defined hereinbefore, and X represents the weight
fraction of Fuel B (the Fisher-Tropsch derived diesel fuel) in the
blend, expressed as a number in the range of from 0 to 1 (i.e.
x=100X). In this Example, the value of A, defined hereinbefore, was
found to equal approximately 16.
* * * * *