U.S. patent application number 10/989589 was filed with the patent office on 2006-05-18 for small off-road engine green fuel.
Invention is credited to Don E. Burnett, Dennis G. Doerr, Nancy W. Eilerts, Eric J. Netemeyer, Richard K. Riley.
Application Number | 20060101712 10/989589 |
Document ID | / |
Family ID | 36384644 |
Filed Date | 2006-05-18 |
United States Patent
Application |
20060101712 |
Kind Code |
A1 |
Burnett; Don E. ; et
al. |
May 18, 2006 |
Small off-road engine green fuel
Abstract
An off-road engine fuel that may comprise less than or equal to
about 1 liquid volume percent aromatic hydrocarbons according to
ASTM D-1319. The fuel may comprise a specific gravity effective for
employment of the fuel in 2-cyle and 4-cycle off-road engines. The
fuel may further comprise a specific gravity according to ASTM
D-4052 from about 0.6 to about 0.8. The fuel may comprise from
about 0.5 to about 50 liquid volume percent naphthenes. The fuel
may be made up of hydrocarbons having from about 4 to about 13
carbon atoms. The fuel may comprise less than or equal to about 1
liquid volume percent olefins according to ASTM D-1319; less than
or equal to about 0.1 liquid volume percent benzene according to
ASTM D-1319; less than or equal to about 10 ppm by weight sulfur
according to ASTM D-5453; equal to or greater than about 85 liquid
volume percent saturated hydrocarbons according to ASTM D-1319; or
combinations thereof. The fuel may also comprise oxygenates; from
about 2 liquid volume percent to about 25 liquid volume percent
oxygenates.
Inventors: |
Burnett; Don E.; (The
Woodlands, TX) ; Doerr; Dennis G.; (Fritch, TX)
; Netemeyer; Eric J.; (Borger, TX) ; Eilerts;
Nancy W.; (Kingwood, TX) ; Riley; Richard K.;
(Friday Harbor, WA) |
Correspondence
Address: |
CHEVRON PHILLIPS CHEMICAL COMPANY
5700 GRANITE PARKWAY, SUITE 330
PLANO
TX
75024-6616
US
|
Family ID: |
36384644 |
Appl. No.: |
10/989589 |
Filed: |
November 15, 2004 |
Current U.S.
Class: |
44/447 |
Current CPC
Class: |
C10L 1/14 20130101; C10L
1/1824 20130101; C10L 1/1852 20130101; C10L 10/02 20130101; C10L
1/023 20130101 |
Class at
Publication: |
044/447 |
International
Class: |
C10L 1/18 20060101
C10L001/18 |
Claims
1. A fuel comprising less than or equal to about 1 liquid volume
percent aromatic hydrocarbons according to ASTM D-1319.
2. The fuel of claim 1 further comprising a specific gravity of
from about 0.6 to about 0.8 according to ASTM D-4052.
3. The fuel of claim 1 further comprising from about 0.5 to about
50 liquid volume percent naphthenes.
4. The fuel of claim 3 wherein the naphthenes comprise substituted
cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, or
combinations thereof.
5. The fuel of claim 3 wherein the naphthenes comprise cyclobutane,
cyclopentane, cyclohexane, cycloheptane, cyclooctane, or
combinations thereof.
6. The fuel of claim 1 further comprising hydrocarbons having from
about 4 to about 13 carbon atoms.
7. The fuel of claim 1 further comprising less than or equal to
about 1 liquid volume percent olefins according to ASTM D-1319.
8. The fuel of claim 1 further comprising less than or equal to
about 0.1 liquid volume percent benzene according to ASTM D-3606,
D-4420, or other available chromatography method.
9. The fuel of claim 1 further comprising less than or equal to
about 10 ppm by weight sulfur according to ASTM D-5453.
10. The fuel of claim 1 further comprising equal to or greater than
about 85 liquid volume percent saturated hydrocarbons according to
ASTM D-1319.
11. The fuel of claim 1 further comprising oxygenates.
12. The fuel of claim 11 wherein the fuel comprises from about 2
liquid volume percent to about 25 liquid volume percent
oxygenates.
13. The fuel of claim 11 wherein the oxygenates comprise tert-butyl
alcohol, n-butanol, methanol, n-propanol, isopropanol, TAME, DIPE,
DNPE, DNBE, ethyl ether, MTBE, ethanol (EtOH), ethyl tert-butyl
ether (ETBE), or combinations thereof.
14. The fuel of claim 1 further comprising from about 0.5 weight
percent to about 5 weight percent oxygen.
15. The fuel of claim 1 further comprising a boiling point range of
from about 90.degree. F. to about 360.degree. F. according to ASTM
D-86.
16. The fuel of claim 1 further comprising an anti-knock index from
about 82 to about 92.
17. The fuel of claim 1 further comprising a Reid Vapor Pressure
appropriate for regular summer gasoline according to ASTM
D-4814.
18. The fuel of claim 1 wherein emissions of benzene,
1,3-butadiene, formaldehyde, and acetaldehyde during engine
operation are at least about 40 percent less than emissions of
benzene, 1,3-butadiene, formaldehyde, and acetaldehyde from a
reference standard fuel according to the 6 mode California Air
Resources Board Small Off Road Engine test.
19. The fuel of claim 1 wherein emissions of benzene during engine
operation are at least about 75 percent less than emissions of
benzene from a reference standard fuel according to the 6 mode
California Air Resources Board Small Off Road Engine test.
20. The fuel of claim 11 wherein emissions of 1,3-butadiene during
engine operation are at least about 20 percent less than emissions
of 1,3-butadiene from a reference standard fuel according to the 6
mode California Air Resources Board Small Off Road Engine test.
21. The fuel of claim 1 wherein emissions of 1,3-butadiene during
operation of a 2-cycle engine are at least about 15 percent less
than emissions of 1,3-butadiene from a reference standard fuel
according to the 6 mode California Air Resources Board Small Off
Road Engine test.
22. The fuel of claim 11 wherein emissions of particulate matter
during operation of a 2-cycle engine are at least about 20 percent
less than emissions of particulate matter from a reference standard
fuel according to the 6 mode California Air Resources Board Small
Off Road Engine test.
23. The fuel of claim 1 wherein emissions of oxides of nitrogen
during operation of a 2-cycle engine are at least about 15 percent
less than emissions of oxides of nitrogen from a reference standard
fuel according to the 6 mode California Air Resources Board Small
Off Road Engine test.
24. The fuel of claim 11 wherein the ozone formation potential of
emissions during operation of a 2-cycle engine are at least about
20 percent less than the ozone formation potential of emissions
from a reference standard fuel according to SAE 930142.
25. The fuel of claim 1 wherein the ozone formation potential of
emissions during operation of a 2-cycle engine are at least about
10 percent less than the ozone formation potential of emissions
from a reference standard fuel according to SAE 930142.
26. The fuel of claim 1 wherein the ozone formation potential of
volatile organic compound emissions during refueling are at least
about 5 percent less than the ozone formation potential of volatile
organic compound emissions from a reference standard fuel according
to SAE 930142.
27. The fuel of claim 11 wherein the ozone formation potential of
emissions during engine operation are at least about 2 percent less
than the ozone formation potential of emissions from a reference
standard fuel according to SAE 930142.
28. The fuel of claim 11 wherein emissions of carbon monoxide
during engine operation are at least about 12 percent less than
emissions of carbon monoxide from a reference standard fuel
according to the 6 mode California Air Resources Board Small Off
Road Engine test.
29. The fuel of claim 11 wherein emissions of hydrocarbons during
engine operation are at least about 1.5 percent less than emissions
of a reference standard fuel according to the 6 mode California Air
Resources Board Small Off Road Engine test.
30. An off-road engine fuel comprising less than or equal to about
1 liquid volume percent aromatic hydrocarbons according to ASTM
D-1319.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
DEVELOPMENT
[0003] Not applicable.
REFERENCE TO A MICROFICHE APPENDIX
[0004] Not applicable.
FIELD OF THE INVENTION
[0005] The present disclosure relates generally to fuels, and in
particular environmentally friendly or "green" fuels. More
particularly, the present disclosure relates to off-road engine
fuels suitable for use in 2-cycle and 4-cycle engines and having
low toxic emissions.
BACKGROUND OF THE INVENTION
[0006] Cleaner alternatives to existing commercial gasoline would
reduce the pollution associated with use of off-road engines such
as 2-cycle and 4-cycle engines, and thereby help to temper
restrictions on use of off-road engines that are being considered.
Consideration has been given to limiting the use of off-road
2-cycle and 4-cycle engines, such as are used in landscape
maintenance, due to pollution and smog generation. For example,
science indicates that the precursors to ozone emitted from these
engines may have less of an impact after 2:00 PM daily. Banning
commercial mowing and landscape maintenance would in many ways
result in a significant and undesirable economic impact. Use of
cleaner fuels in any small, off-road engines, such as used in
snowmobiles, jet skis, portable generators, 2-wheel and 4-wheel
all-terrain vehicles, chain saws, wood chippers, and the like,
would help counteract any negative economic impact while reducing
pollution. In addition to reducing pollution, cleaner fuels would
reduce toxin and exhaust emissions, which would reduce harmful
effects on the operators of such off-road engines. Thus, an ongoing
need exists for cleaner, affordable off-road engine fuels that
reduce levels of pollutants and toxins.
SUMMARY OF THE INVENTION
[0007] In various embodiments, provided is an off-road engine fuel
comprising less than or equal to about 1 liquid volume percent
aromatic hydrocarbons according to ASTM D-1319. In embodiments, the
fuel may further comprise a specific gravity effective for
employment of the fuel in 2-cycle and 4-cycle off-road engines. In
other embodiments, the fuel may further comprise a specific gravity
according to ASTM D-4052 from about 0.6 to about 0.8. The fuel may
further comprise from about 0.5 to about 50 liquid volume percent
naphthenes. In embodiments, the fuel comprises hydrocarbons having
from about 4 to about 13 carbon atoms. In some embodiments the fuel
further comprises less than or equal to about 1 liquid volume
percent olefins according to ASTM D-1319; less than or equal to
about 0.1 liquid volume percent benzene according to ASTM D-1319;
less than or equal to about 10 ppm by weight sulfur according to
ASTM D-5453; equal to or greater than about 85 liquid volume
percent saturated hydrocarbons according to ASTM D-1319; or
combinations thereof. The fuel may also comprise oxygenates; for
example from about 2 liquid volume percent to about 25 liquid
volume percent oxygenates.
[0008] In embodiments, combustion of the fuel yields emissions of
benzene, 1,3-butadiene, formaldehyde, and acetaldehyde during
engine operation that are at least about 40 percent less than
emissions of benzene, 1,3-butadiene, formaldehyde, and acetaldehyde
from combustion of a reference standard fuel according to the 6
mode California Air Resources Board Small Off Road Engine test.
Further, the fuel may yield emissions of benzene during engine
operation that are at least about 75 percent less than emissions of
benzene from a reference standard fuel according to the 6 mode
California Air Resources Board Small Off Road Engine test;
emissions of 1,3-butadiene from an oxygenated fuel during engine
operation that are at least about 20 percent less than emissions of
1,3-butadiene from a reference standard fuel according to the 6
mode California Air Resources Board Small Off Road Engine test;
emissions of 1,3-butadiene during operation of a 2-cycle engine
that are at least about 15 percent less than emissions of
1,3-butadiene from a reference standard fuel according to the 6
mode California Air Resources Board Small Off Road Engine test;
emissions of particulate matter from an oxygenated fuel during
operation of a 2-cycle engine that are at least about 20 percent
less than emissions of particulate matter from a reference standard
fuel according to the 6 mode California Air Resources Board Small
Off Road Engine test; emissions of oxides of nitrogen during
operation of a 2-cycle engine that are at least about 15 percent
less than emissions of oxides of nitrogen from a reference standard
fuel according to the 6 mode California Air Resources Board Small
Off Road Engine test; emissions of carbon monoxide from an
oxygenated fuel during engine operation that are at least about 12
percent less than emissions of carbon monoxide from a reference
standard fuel according to the 6 mode California Air Resources
Board Small Off Road Engine test; emissions of hydrocarbons from an
oxygenated fuel during engine operation are at least about 1.5
percent less than emissions of a reference standard fuel according
to the 6 mode California Air Resources Board Small Off Road Engine
test; or combinations thereof.
[0009] In various embodiments, a method disclosed comprises
selecting a first hydrocarbon stream comprising equal to or greater
than about 99 liquid volume percent saturated hydrocarbons having
from about 4 to about 9 carbon atoms; combining from about 5 liquid
volume percent to about 85 liquid volume percent of the first
hydrocarbon stream with from about 2 liquid volume percent to about
10 liquid volume percent of a second hydrocarbon stream comprising
at least about 50 weight percent naphthenes; and formulating an
off-road engine fuel from a mixture comprising the first
hydrocarbon stream and second hydrocarbon stream. In further
embodiments, the first hydrocarbon stream is combined with from
about 0 liquid volume percent to about 25 liquid volume percent of
an oxygenate; with a third hydrocarbon stream comprising equal to
or greater than about 99.5 liquid volume percent saturated
hydrocarbons having from about 6 to about 8 carbon atoms; with from
about 0 liquid volume percent to about 10 liquid volume percent of
an n-butane stream; with from about 0 liquid volume percent to
about 10 liquid volume percent of an isopentane stream; with from
about 0 liquid volume percent to about 20 liquid volume percent of
an isohexane stream; with from about 0 liquid volume percent to
about 25 liquid volume percent of a heptane stream; with from about
0 liquid volume percent to about 25 liquid volume percent of a
fourth hydrocarbon stream comprising at least 99 weight percent
isoparaffins having from about 9 to about 11 carbon atoms; with oil
for use of the off-road engine fuel in an engine; or combinations
thereof.
[0010] In some embodiments, a method is provided for packaging the
fuel in units of less than or equal to about 10 gallons; and
selling the fuel for use in off-road 2-cycle and 4-cycle engines.
The method may further comprise selling the fuel in retail
stores.
DETAILED DESCRIPTION OF EMBODIMENTS
[0011] Described herein are off-road engine fuels ("fuels" or
"green fuels") and methods of formulating and using such fuels.
Such off road fuels are appropriate for use in commercially
available 2-cycle and 4-cycle off-road engines. An off-road engine
fuel in accordance with the present disclosure may comprise a
mixture (or "blend") of various hydrocarbon streams having
hydrocarbons with from about 4 to about 13 carbon atoms. The
particular hydrocarbon streams (i.e., fuel constituents,
feedstocks, or blendstocks) combined to form the fuel are generally
selected such that the fuel has desirable physical properties,
composition, combustion characteristics, or combinations thereof as
described herein.
[0012] In an embodiment, the fuel has a Reid vapor pressure (RVP)
that is appropriate for `regular summer gasoline` as the term is
known to a person skilled in the art, alternatively an RVP of from
about 7 to about 9 pounds according to ASTM D-4814. In embodiments,
the fuel comprises a boiling point range from about 90 to about 360
degrees Fahrenheit according to ASTM D-86. Further, the fuel
constituents may be selected such that the fuel possesses an
anti-knock index, or (R+M)/2 octane, that falls within a range from
about 82 to about 92.
[0013] The specific gravity of the fuel may impact its operability
in commercially available 2-cycle and 4-cycle engines. In an
embodiment, the off-road engine fuel described herein comprises a
specific gravity effective for employment of the fuel in commercial
2-cycle and 4-cycle off-road engines; alternatively, the fuel
comprises a specific gravity according to ASTM D-4052 of from about
0.6 to about 0.8; alternatively, the specific gravity is from about
0.65 to about 0.75; alternatively, from about 0.675 to about 0.725.
The specific gravity may be adjusted depending upon the particular
combination of hydrocarbons present in the fuel.
[0014] In an embodiment, the green fuel comprises equal to or
greater than about 50 mole percent paraffins having from about 4 to
about 13 carbon atoms, and equal to or greater than about 2 mole
percent naphthenes having from about 4 to about 12 carbon atoms;
alternatively, equal to or greater than about 75 mole percent
paraffins and equal to or greater than about 6 mole percent
naphthenes; alternatively, equal to or greater than about 85 mole
percent paraffins and equal to or greater than about 11 mole
percent naphthenes. As used herein, paraffins may include
isoparaffins. In another embodiment, the fuel comprises less than
or equal to 5 mole percent aromatic hydrocarbons; alternatively,
less than or equal to 1 mole percent; alternatively, less than or
equal to 0.5 mole percent. In another embodiment, the fuel
comprises less than or equal to 5 mole percent olefins;
alternatively, less than or equal to 1 mole percent; alternatively,
less than or equal to 0.5 mole percent. In an embodiment, a green
fuel has a hydrocarbon distribution equal or similar to that shown
in Table 1, alternatively .+-.5 percent, alternatively .+-.3
percent, alternatively .+-.1 percent. TABLE-US-00001 TABLE 1 Green
Fuel Hydrocarbon Distribution Component % MOL % WT C4 4.450 2.612
C5 20.557 14.800 C6 15.468 13.458 C7 18.530 18.745 C8 26.608 30.677
C9 6.885 8.879 C10 6.919 9.914 C11 0.572 0.897 C12 0.011 0.020
[0015] In another embodiment, a green fuel comprises the properties
shown in Table 2. TABLE-US-00002 TABLE 2 Example Green Fuel
Properties Test Method Results Specific Gravity, 60/60 ASTM D-4052
0.6975 Sulfur, ppm ASTM D-2622 1.2 Corrosion, 3 hr @ 50.degree. C.
ASTM D-3231 1A Oxygen Content, wt % 0 Hydrogen, wt % 16.013 Carbon,
wt % 83.923 Net Heat of Combustion ASTM D-240 19270 Existent Gums
(mg/100 ml) ASTM D-381 0.9 Existent Gums ASTM D-381 0.01 (mg/100
ml)(washed) Reid Vapor Pressure (psi) ASTM D-6378 7.02 TEL, mg/l
ASTM D-3237 <0.0008 Benzene Content, lv % 0 Distillation
.degree. F. ASTM D-86 IBP 105.3 5% 131.2 10% 141.6 20% 158.0 30%
172.8 40% 187.7 50% 203.5 60% 219.4 70% 237.4 80% 262.2 90% 303.6
95% 323.1 EP 339.3 Loss 1.1 Residue 1.0 Hydrocarbon Type, lv % ASTM
D-1319 Aromatics 0.5 Olefins 0.5 Saturates 99.0 Research Octane No.
ASTM D-2699 90.3 Motor Octane No. ASTM D-2700 88.8 Antiknock Index
89
[0016] In some embodiments, inclusion of an oxygenate in the fuel
reduces emissions from the fuel during engine operation. In
embodiments, the oxygenated green fuel comprises from about 2 to
about 25 liquid volume percent oxygenates; alternatively, from
about 8 to about 17 liquid volume percent oxygenates;
alternatively, from about 10 to about 14 liquid volume percent
oxygenates. In terms of oxygen content, in embodiments the fuel may
comprise from about 0.5 to about 5 weight percent oxygen;
alternatively, from about 1 to about 3.5 weight percent oxygen;
alternatively, from about 1.7 to about 2.7 weight percent oxygen.
Suitable oxygenates may comprise tert-butyl alcohol, n-butanol,
methanol, n-propanol, isopropanol, TAME, DIPE, DNPE, DNBE, ethyl
ether, MTBE, ethanol (EtOH), ethyl tert-butyl ether (ETBE), or
combinations thereof. In certain embodiments, the oxygenates
comprise EtOH, ETBE, or combinations thereof.
[0017] In embodiments comprising oxygenates, the oxygenated fuel
may comprise equal to or greater than about 50 mole percent
paraffins having from about 4 to about 13 carbon atoms, equal to or
greater than about 2 mole percent naphthenes having from about 4 to
about 12 carbon atoms, and equal to or greater than about 3 mole
percent oxygenates; alternatively, equal to or greater than about
65 mole percent paraffins, equal to or greater than about 4 mole
percent naphthenes, and equal to or greater than about 8 mole
percent oxygenates; alternatively, equal to or greater than about
77 mole percent paraffins, equal to or greater than about 6 mole
percent naphthenes, and equal to or greater than about 12 mole
percent oxygenates. In an embodiment, an oxygenated green fuel has
a hydrocarbon distribution equal or similar to that shown in Table
3, alternatively .+-.5 percent, alternatively .+-.3 percent,
alternatively .+-.1 percent. TABLE-US-00003 TABLE 3 Oxygenated
Green Fuel Hydrocarbon Distribution Component % MOL % WT C4 5.833
3.377 C5 14.021 10.013 C6 21.666 20.625 C7 24.319 24.264 C8 20.791
23.651 C9 6.396 8.137 C10 6.434 9.094 C11 0.528 0.817 C12 0.012
0.021
[0018] In another embodiment, an oxygenated green fuel comprises
the properties exhibited in Table 4. TABLE-US-00004 TABLE 4 Example
Oxygenated Green Fuel Properties Test Method Results Specific
Gravity, 60/60 ASTM D-4052 0.7016 Sulfur, ppm ASTM D-2622 1.0
Corrosion, 3 hr @ 50.degree. C. ASTM D-3231 1A Oxygen Content, wt %
1.92 Hydrogen, wt % 15.759 Carbon, wt % 82.054 ETBE, vol %
Chromatography 11.81 Net Heat of Combustion ASTM D-240 18790
Existent Gums (mg/100 ml) ASTM D-381 1.5 Existent Gums ASTM D-381
1.4 (mg/100 ml)(washed) Reid Vapor Pressure (psi) ASTM D-6378 7.15
TEL, mg/l ASTM D-3237 <0.0008 Benzene Content, vol % 0
Distillation .degree. F. ASTM D-86 IBP 102.0 5% 129.9 10% 143.1 20%
162.0 30% 176.5 40% 189.0 50% 200.7 60% 213.6 70% 231.4 80% 257.7
90% 304.0 95% 324.9 EP 343.2 Loss 1.0 Residue 1.2 Hydrocarbon Type,
vol % ASTM D-1319 Aromatics 0.5 Olefins 0.6 Saturates 98.9 Research
Octane No. ASTM D-2699 91 Motor Octane No. ASTM D-2700 88.5
Antiknock Index 90
[0019] Hydrocarbon streams that make up the off-road engine fuel
are selected such that the fuel comprises limited levels of one or
more pollutants and toxic compounds. In various embodiments, the
fuel may comprise from about 0 to about 10 liquid volume percent
aromatic hydrocarbons according to ASTM D-1319; alternatively, less
than or equal to about 1 liquid volume percent aromatic
hydrocarbons; alternatively, less than or equal to about 0.5 liquid
volume percent aromatic hydrocarbons. In other embodiments, the
fuel may comprise from about 0 to about 10 liquid volume percent
olefins according to ASTM D-1319; alternatively, less than or equal
to about 1 liquid volume percent olefins; alternatively, less than
or equal to about 0.5 liquid volume percent olefins. In yet other
embodiments, the fuel may comprise from about 0 to about 1 liquid
volume percent benzene according to ASTM D-3606, D-4420, or other
available chromatography method; alternatively, less than or equal
to about 0.1 liquid volume percent benzene; alternatively, less
than or equal to about 0.05 liquid volume percent benzene. In still
other embodiments, the fuel may comprise less than or equal to
about 10 parts per million by weight sulfur according to ASTM
D-5453; alternatively, about 5 parts per million by weight sulfur;
alternatively, about 1.5 parts per million by weight. In
embodiments, the fuel may comprise any number of combinations of
the above limited levels of aromatic hydrocarbons, olefins,
benzene, and sulfur.
[0020] The level of saturation among the hydrocarbons in the fuel
may be indicative of the lack of pollutants and toxins in the fuel.
In embodiments, the fuel comprises equal to or greater than about
85 liquid volume percent saturated hydrocarbons according to ASTM
D-1319; alternatively, equal to or greater than about 90 liquid
volume percent; alternatively, equal to or great than about 98
liquid volume percent.
[0021] In embodiments, the fuel comprises from about 0.5 to about
50 liquid volume percent naphthenes; alternatively, from about 2 to
about 20 liquid volume percent naphthenes; alternatively, from
about 5 to about 14 liquid volume percent. In some embodiments,
naphthenes comprise various substituted cyclic hydrocarbons,
un-substituted cyclic hydrocarbons, or combinations thereof. In
certain embodiments, naphthenes comprise cyclobutane, cyclopentane,
cyclohexane, cycloheptane, cyclooctane, or combinations
thereof.
[0022] In various embodiments, use of the green fuel in various
engines reduces emissions of certain toxic compounds during
combustion as compared to the emissions from a reference standard
fuel (or "reference fuel"). Such a reference fuel may be, for
example, a fluid designated by a governmental or regulatory agency
as being acceptable for common private and commercial use in
commercially available 2-cycle and 4-cycle engines. In embodiments,
the reference fuel comprises an RVP in compliance with ASTM D-4814,
the governing specification for commercial gasoline in the United
States. In other embodiments, the reference fuel meets the
certification standards for a regular commercial gasoline according
to ASTM D-1319. In certain embodiments, the reference fuel exhibits
the composition and properties provided in Tables 5a and 5b wherein
IBP represents initial boiling point and EP represents end point:
TABLE-US-00005 TABLE 5A Example Properties of a Suitable Reference
Fuel Test Specification Method Specific Gravity, 60/60 0.7343-0.744
ASTM D-4052 API Gravity Report ASTM D-1298 Phosphorous, g/gl 0.002
max ASTM D-3231 Sulfur, ppm 1000 max ASTM D-2622 Reid Vapor
Pressure 8.8-9.2 ASTM D-6378 Lead (ml/gal) 0.005 max ASTM D-3237
Aromatics, vol % 35 max ASTM D-1319 Olefins, vol % 10 max ASTM
D-1319 Research Octane Number 91 + 0.7 ASTM D-2699 Anti Knock Index
87 max
[0023] TABLE-US-00006 TABLE 5b Example Distillation Data for a
Suitable Reference Fuel, .degree. F., ASTM D-86 IBP 75-95 50%
200-230 90% 300-325 EP 415 max Loss 1.4 Residue 1
An example of a suitable reference fuel is the Unleaded Test
Gasoline Regular Grade (UTG-91) manufactured by Chevron Phillips
Chemical Company.
[0024] In embodiments, emissions of certain EPA-designated toxic
compounds from the green fuel during engine operation are less than
emissions of similar toxic compounds from the reference fuel. In
some embodiments, emissions of benzene, 1,3-butadiene,
formaldehyde, and acetaldehyde from the green fuel during engine
operation are less than emissions of the same toxic compounds from
the reference fuel according to the 6 mode California Air Resources
Board Small Off Road Engine Test (CARBT). In certain embodiments,
emissions of benzene, 1,3-butadiene, formaldehyde, and acetaldehyde
from the green fuel during engine operation are at least about 40
percent less than emissions of the same toxic compounds from the
reference fuel according to CARBT; alternatively, emissions of such
compounds are at least about 45 percent less than similar emissions
from the reference fuel; alternatively, emissions are at least
about 55 percent less.
[0025] In an embodiment, emissions of benzene from the green fuel
during engine operation are at least about 75 percent less than
emissions of benzene from the reference standard fuel according to
CARBT; alternatively, at least about 80 percent less;
alternatively, at least about 88 percent less. In an embodiment,
emissions of 1,3-butadiene from the oxygenated green fuel during
engine operation are at least about 20 percent less than emissions
of 1,3-butadiene from the reference standard fuel according to
CARBT; alternatively, at least about 30 percent less;
alternatively, at least about 40 percent less. In an embodiment,
emissions of 1,3-butadiene from the green fuel during operation of
a 2-cycle engine are at least about 15 percent less than emissions
of 1,3-butadiene from the reference standard fuel according to
CARBT; alternatively, at least about 20 percent less;
alternatively, at least about 23 percent less.
[0026] Use of the green fuel and oxygenated green fuel may further
reduce emissions of other compounds, such as particulate matter,
oxides of nitrogen, carbon monoxide, and hydrocarbons. In an
embodiment, emissions of particulate matter from the green fuel
during operation of a 2-cycle engine are at least about 2 percent
less than emissions of particulate matter from the reference
standard fuel according to CARBT; alternatively, at least about 3
percent less; alternatively, at least about 4.7 percent less. In an
embodiment, emissions of particulate matter from the oxygenated
green fuel during operation of a 2-cycle engine are at least about
20 percent less than emissions of particulate matter from the
reference standard fuel according to CARBT; alternatively, at least
about 25 percent less; alternatively, at least about 28 percent
less. In an embodiment, emissions of oxides of nitrogen from the
green fuel during operation of a 2-cycle engine are at least about
15 percent less than emissions of oxides of nitrogen from the
reference standard fuel according to CARBT; alternatively, at least
about 20 percent less; alternatively, at least about 24 percent
less. In an embodiment, emissions of carbon monoxide from the
oxygenated green fuel during engine operation are at least about 12
percent less than emissions of carbon monoxide from the reference
standard fuel according to CARBT; alternatively, at least about 17
percent less; alternatively, at least about 22 percent less. In an
embodiment, emissions of hydrocarbons from the oxygenated green
fuel during engine operation are at least about 1.5 percent less
than emissions of hydrocarbons from the reference standard fuel
according to CARBT; alternatively, at least about 5 percent less;
alternatively, at least about 9 percent less.
[0027] Use of the green fuel and oxygenated green fuel may also
reduce the ozone formation potential of emissions and,
specifically, volatile organic compound (VOC) emissions, during
engine operation and refueling. In an embodiment, the ozone
formation potential of emissions from the oxygenated green fuel
during engine operation is at least about 2 percent less than the
ozone formation potential of emissions from the reference standard
fuel according to the test method described by Siegl, Walter O., et
al, "Improved Speciation Methodology for Phase III for the Auto/oil
Air Quality Improvement Research Program," SAE 930142, 1993 (or
"SAE 930142"); alternatively, at least about 15 percent less;
alternatively, at least about 29 percent less. In an embodiment,
the ozone formation potential of emissions from the oxygenated
green fuel during operation of a 2-cycle engine is at least about
20 percent less than the ozone formation potential of emissions
from the reference standard fuel according to SAE 930142;
alternatively, at least about 25 percent less; alternatively, at
least about 27 percent less. In an embodiment, the ozone formation
potential of emissions from the green fuel during operation of a
2-cycle engine is at least about 10 percent less than the ozone
formation potential of emissions from the reference standard fuel
according to SAE 930142; alternatively, at least about 15 percent
less; alternatively, at least about 18 percent less. In an
embodiment, the ozone formation potential of VOC emissions from the
green fuel during refueling is at least about 5 percent less than
the ozone formation potential of VOC emissions from the reference
standard fuel according to SAE 930142; alternatively, at least
about 8 percent less; alternatively, at least about 11.5 percent
less.
[0028] An off-road engine fuel in accordance with the present
disclosure may comprise a mixture (or "blend") of various
hydrocarbon streams having hydrocarbons with from about 4 to about
13 carbon atoms. The particular hydrocarbon streams (i.e., fuel
constituents, feedstocks, or blendstocks) combined to form the fuel
are generally selected such that the fuel has a desired combination
of physical properties, composition, combustion characteristics, or
combinations thereof as described herein.
[0029] In embodiments, a first hydrocarbon stream employed in
formulating the green fuel comprises hydrocarbons having from about
4 to about 9 carbon atoms. In certain embodiments, the first
hydrocarbon stream is a HF light alkylate stream comprising
hydrocarbons having from about 4 to about 9 carbon atoms. In an
embodiment, a first hydrocarbon stream has a hydrocarbon
distribution equal or similar to that shown in Table 6,
alternatively .+-.5 weight percent, alternatively .+-.3 weight
percent, alternatively .+-.1 weight percent. TABLE-US-00007 TABLE 6
Hydrocarbon Distribution in First Hydrocarbon Stream Compound
Weight Percent C4 0.5 C5 9.1 C6 3.9 C7 22.5 C8 56.8 C9 3.9 C10 2.8
C11 0.5
[0030] In another embodiment, a first hydrocarbon stream comprises
the properties shown in Table 7. TABLE-US-00008 TABLE 7 Example
Properties of a First Hydrocarbon Stream Test Method Results
Specific Gravity, 60/60 ASTM D-4052 0.6943 Sulfur, ppm ASTM D-5453
1.8 Reid Vapor Pressure (psi) ASTM D-6378 5.13 Distillation,
.degree. F. ASTM D-86 IBP 104.7 5% 153.7 10% 169.9 20% 187.9 30%
198.1 40% 204.6 50% 208.9 60% 212.7 70% 216.7 80% 222.1 90% 233.4
95% 252.1 EP 301.3 Loss 0.8 Residue 1.0 Hydrocarbon Type, vol %
ASTM D-1319 Aromatics 0.2 Olefins 0 Saturates 99.8
[0031] In some embodiments, the first hydrocarbon stream employed
in formulating the green fuel comprises less than or equal to about
10 parts per million by weight sulfur according to ASTM D-5453;
alternatively, about 5 parts per million by weight sulfur;
alternatively, about 2 parts per million by weight. In embodiments,
the first hydrocarbon stream further comprises from about 0 to
about 5 liquid volume percent aromatic hydrocarbons according to
ASTM D-1319; alternatively, less than or equal to about 1 liquid
volume percent aromatic hydrocarbons; alternatively, less than or
equal to about 0.5 liquid volume percent aromatic hydrocarbons. In
other embodiments, the first hydrocarbon stream further comprises
from about 0 to about 5 liquid volume percent olefins according to
ASTM D-1319; alternatively, less than or equal to about 1 liquid
volume percent olefins; alternatively, less than or equal to about
0.5 liquid volume percent olefins. In yet other embodiments, the
first hydrocarbon stream further comprises from about 0 to about 1
liquid volume percent benzene according to ASTM D-3606, D-4420, or
other available chromatography method; alternatively, less than or
equal to about 0.1 liquid volume percent benzene; alternatively,
less than or equal to about 0.05 liquid volume percent benzene.
[0032] In various embodiments, a second hydrocarbon stream
comprising naphthenes is employed in formulating the green fuel. In
some embodiments, the second hydrocarbon stream comprises
substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons,
or combinations thereof. In certain embodiments, the second
hydrocarbon stream comprises naphthenes having from about 4 to
about 11 carbon atoms. In other embodiments, naphthenes in the
second hydrocarbon stream comprise substituted naphthenes,
cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane,
or combinations thereof. In an embodiment, naphthenes in the second
hydrocarbon stream comprise the properties shown in Table 8.
TABLE-US-00009 TABLE 8 Example Properties of Naphthenes in a
Suitable Second Hydrocarbon Stream Test Method Results Sulfur, ppm
ASTM D-4045 1.1 GC Analysis, wt % Chromatography Cyclopentane 79.80
2,2-Dimethylbutane 15 n-Pentane 5
[0033] In some embodiments, a third hydrocarbon stream is employed
in formulating the green fuel. In embodiments, the third
hydrocarbon stream comprises equal to or greater than about 99.5
liquid volume percent saturated hydrocarbons having from about 6 to
about 8 carbon atoms. In an embodiment, a third hydrocarbon stream
has a hydrocarbon distribution equal or similar to that shown in
Table 9, alternatively .+-.5 weight percent, alternatively .+-.3
weight percent, alternatively .+-.1 weight percent. TABLE-US-00010
TABLE 9 Hydrocarbon Distribution in Third Hydrocarbon Stream
Compound Weight Percent C4 0.9 C5 17.0 C6 6.4 C7 18.6 C8 43.6 C9
7.3 C10 5.2 C11 0.9
[0034] In another embodiment, a third hydrocarbon stream comprises
the properties shown in Table 10. TABLE-US-00011 TABLE 10 Example
Properties of a Third Hydrocarbon Stream Test Method Results
Specific Gravity, 60/60 F ASTM D-4052 0.6971 API Gravity ASTM
D-5453 0.5 Distillation .degree. F., ASTM D-86 IBP 104.4 5% 143.6
10% 157.5 20% 178.0 30% 194.0 40% 206.4 50% 216.3 60% 225.9 70%
236.8 80% 248.9 90% 273.2 95% 298.9 EP 331.3 Hydrocarbon Type, vol
% ASTM D-1319 Aromatics 0 Olefins 0 Saturates 100
[0035] In certain embodiments, the third hydrocarbon stream further
comprises from about 0 to about 2 liquid volume percent aromatic
hydrocarbons according to ASTM D-1319; alternatively, less than or
equal to about 1 liquid volume percent aromatic hydrocarbons;
alternatively, less than or equal to about 0.5 liquid volume
percent aromatic hydrocarbons. In other embodiments, the third
hydrocarbon stream further comprises from about 0 to about 2 liquid
volume percent olefins according to ASTM D-1319; alternatively,
less than or equal to about 1 liquid volume percent olefins;
alternatively, less than or equal to about 0.5 liquid volume
percent olefins. In yet other embodiments, the third hydrocarbon
stream further comprises from about 0 to about 0.5 liquid volume
percent benzene according to ASTM D-3606, D-4420, or other
available chromatography method; alternatively, less than or equal
to about 0.1 liquid volume percent benzene; alternatively, less
than or equal to about 0.05 liquid volume percent benzene.
[0036] In embodiments, a n-butane stream is employed in formulating
the green fuel. In an embodiment, the n-butane stream comprises at
least about 80 weight percent n-butane; alternatively, at least
about 90 weight percent n-butane; alternatively, at least about 95
weight percent n-butane. In an embodiment, a n-butane stream has a
hydrocarbon distribution equal or similar to that shown in Table
11, alternatively .+-.5 weight percent, alternatively .+-.3 weight
percent, alternatively .+-.1 weight percent. TABLE-US-00012 TABLE
11 Hydrocarbon Distribution in n-Butane Stream Compound Weight
Percent C3 0.5 n-Butane 95.5 Isobutane 3.5 C5 and higher 1.5
[0037] In embodiments, an isopentane stream is employed in
formulating the green fuel. In an embodiment, the isopentane stream
comprises at least about 70 weight percent isopentane;
alternatively, at least about 85 weight percent isopentane;
alternatively, at least about 96 weight percent isopentane. In an
embodiment, an isopentane stream has a hydrocarbon distribution
equal or similar to that shown in Table 12, alternatively .+-.5
weight percent, alternatively .+-.3 weight percent, alternatively
.+-.1 weight percent. TABLE-US-00013 TABLE 12 Hydrocarbon
Distribution in Isopentane Stream Component Weight % isopentane
99.3 n-pentane 0.5 butane 0.2
[0038] In embodiments, an isohexane stream is employed in
formulating the green fuel. In an embodiment, the isohexane stream
comprises at least about 80 weight percent isohexanes;
alternatively, at least about 90 weight percent isohexanes;
alternatively, at least about 99 weight percent isohexanes;
alternatively, about 100 weight percent isohexanes.
[0039] In embodiments, a heptane stream is employed in formulating
the green fuel. In an embodiment, the heptane stream comprises at
least about 50 weight percent heptanes; alternatively, at least
about 70 weight percent heptanes; alternatively, at least about 80
weight percent heptanes. For purposes of the present application,
"heptanes" refers to both normal heptane and isomers of heptane. In
an embodiment, a heptane stream has a hydrocarbon distribution
equal or similar to that shown in Table 13, alternatively .+-.5
weight percent, alternatively .+-.3 weight percent, alternatively
.+-.1 weight percent. TABLE-US-00014 TABLE 13 Hydrocarbon
Distribution in Heptane Stream Component Liquid Volume % toluene
2.78 benzene (ppm) 2.3 2-methylhexane 23.5 3-methylhexane 30.5
n-heptane 26.5
[0040] In another embodiment, a heptane stream comprises the
properties shown in Table 14. TABLE-US-00015 TABLE 14 Example
Properties of a Heptane Stream Test Method Results Specific
Gravity, 60/60 ASTM D-4052 0.697 Doctor ASTM D-235 Negative Sulfur,
ppm ASTM D-4045 0.1 Nonvolatile Matter (mg/100 ml) ASTM D-1353 0.1
Saybolt Color ASTM D-6045 +30 Corrosion (1 hr@100.degree. F.) ASTM
D-130 1A Distillation ASTM D-86 Initial Boiling Point .degree. F.
196 Dry Point .degree. F. 202 GC Analysis Chromatography Toluene,
vol % 2.78 Benzene, ppm 2.2 2-Methylhexane, vol % 23.5
3-Methylhexane, vol % 30.5 n-Heptane, vol % 26.5
[0041] In some embodiments, a fourth hydrocarbon stream is employed
in formulating the green fuel. In embodiments, the fourth
hydrocarbon stream comprises at least about 99 weight percent
isoparaffins having from about 9 to about 11 carbon atoms. In an
embodiment, a fourth hydrocarbon stream has a hydrocarbon
distribution equal or similar to that shown in Table 15,
alternatively .+-.5 weight percent, alternatively .+-.3 weight
percent, alternatively .+-.1 weight percent. TABLE-US-00016 TABLE
15 Hydrocarbon Distribution in Fourth Hydrocarbon Stream Component
Weight % C8 3 C9 14 C10 62 C11 20
[0042] In certain embodiments, the fourth hydrocarbon stream
further comprises from about 0 to about 2 liquid volume percent
aromatic hydrocarbons according to ASTM D-1319; alternatively, less
than or equal to about 1 liquid volume percent aromatic
hydrocarbons; alternatively, less than or equal to about 0.05
liquid volume percent aromatic hydrocarbons. In other embodiments,
the fourth hydrocarbon stream further comprises from about 0 to
about 2 liquid volume percent olefins according to ASTM D-1319;
alternatively, less than or equal to about 1 liquid volume percent
olefins; alternatively, less than or equal to about 0.05 liquid
volume percent olefins. In yet other embodiments, the fourth
hydrocarbon stream further comprises from about 0 to about 0.5
liquid volume percent benzene according to ASTM D-3606, D-4420, or
other available chromatography method; alternatively, less than or
equal to about 0.1 liquid volume percent benzene; alternatively,
less than or equal to about 0.05 liquid volume percent benzene.
[0043] In some embodiments, a fifth hydrocarbon stream is employed
in formulating the green fuel. In embodiments, the fifth
hydrocarbon stream comprises at least about 99 weight percent
isoparaffins having from about 11 to about 13 carbon atoms. In an
embodiment, a fifth hydrocarbon stream has a hydrocarbon
distribution equal or similar to that shown in Table 16,
alternatively .+-.5 weight percent, alternatively .+-.3 weight
percent, alternatively .+-.1 weight percent. TABLE-US-00017 TABLE
16 Hydrocarbon Distribution in Fifth Hydrocarbon Stream Component
Weight % C10 2 C11 52 C12 42 C13 5
[0044] With the teachings provided in the present application one
of skill in the art will recognize that many combinations of
various hydrocarbon streams may be mixed to achieve the
characteristics of the disclosed green fuel. Further, the source or
sources of the hydrocarbon streams, and the sequence and timing
with which the hydrocarbon streams are combined, may be selected to
obtain a desired quality of the fuel (e.g., physical properties,
composition, combustion characteristics, or combinations thereof).
The particular combination, source(s), sequence, and timing
employed in formulating the fuel may be driven by practical and/or
cost considerations, such as feedstock availability, plant
layout/design, and the like. Thus, the invention disclosed in the
present application is not limited to the specific embodiments and
examples of formulations, blendstocks, and blending sequences
described. In various embodiments, the green fuel is formulated by
combining one or more hydrocarbon streams comprising fully
saturated hydrocarbons having from about 4 to about 13 carbon atoms
with one or more hydrocarbon streams comprising naphthenes having
from about 4 to about 11 carbon atoms. Examples of such hydrocarbon
streams introduced herein are the first hydrocarbon stream, second
hydrocarbon stream, third hydrocarbon stream, fourth hydrocarbon
stream, heptane stream, isopentane stream, isohexane stream, and
n-butane stream.
[0045] In some embodiments, a method is disclosed comprising
selecting a first hydrocarbon stream comprising equal to or greater
than about 99 liquid volume percent hydrocarbons having from about
4 to about 9 carbon atoms; combining from about 5 liquid volume
percent to about 85 liquid volume percent of the first hydrocarbon
stream with from about 2 liquid volume percent to about 10 liquid
volume percent of a second hydrocarbon stream comprising at least
about 50 weight percent naphthenes; and formulating the off-road
engine fuel from a mixture comprising the first hydrocarbon stream
and second hydrocarbon stream.
[0046] In embodiments, the fuel is further combined with from about
0 to about 25 liquid volume percent oxygenate; alternatively, from
about 8 to about 17 liquid volume percent oxygenate; alternatively,
from about 10 to about 14 liquid volume percent oxygenate. In an
embodiment, the fuel is further combined with ETOH, ETBE, or
combinations thereof.
[0047] In some embodiments, from about 5 to about 85 liquid volume
percent of a third hydrocarbon stream is added to a green fuel
formulation; alternatively, from about 25 to about 50 liquid volume
percent of a third hydrocarbon stream is added; alternatively, from
about 30 to about 40 liquid volume percent of a third hydrocarbon
stream is added. In an embodiment, the third hydrocarbon stream
comprises equal to or greater than about 99.5 liquid volume percent
saturated hydrocarbons having from about 6 to about 8 carbon
atoms.
[0048] In embodiments, from about 0 to about 10 liquid volume
percent of a n-butane stream is added to a green fuel formulation;
alternatively, from about 0.75 to about 5 liquid volume percent of
a n-butane stream is added; alternatively, from about 1 to about 3
liquid volume percent of a n-butane stream is added.
[0049] In other embodiments, from about 0 to about 10 liquid volume
percent of an isopentane stream is added to a green fuel
formulation; alternatively, from about 1 to about 5 liquid volume
percent of an isopentane stream is added; alternatively, from about
2 to about 4 liquid volume percent of an isopentane stream is
added.
[0050] In still other embodiments, from about 0 to about 20 liquid
volume percent of an isohexane stream is added to a green fuel
formulation; alternatively, from about 3 to about 16 liquid volume
percent of an isohexane stream is added; alternatively, from about
7 to about 12 liquid volume percent of an isohexane stream is
added.
[0051] In yet other embodiments, from about 0 to about 25 liquid
volume percent of a heptane stream is added to a green fuel
formulation; alternatively, from about 3 to about 18 liquid volume
percent of a heptane stream is added; alternatively, from about 7
to about 12 liquid volume percent of a heptane stream is added.
[0052] In some embodiments, from about 0 to about 25 liquid volume
percent of a fourth hydrocarbon stream is added to a green fuel
formulation; alternatively, from about 4 to about 20 liquid volume
percent of a fourth hydrocarbon stream is added; alternatively,
from about 8 to about 14 liquid volume percent of a fourth
hydrocarbon stream is added. In an embodiment, the fourth
hydrocarbon stream comprises equal to or greater than about 99
weight percent isoparaffins having from about 9 to about 11 carbon
atoms.
[0053] In some embodiments, from about 0 to about 5 liquid volume
percent of a fifth hydrocarbon stream is added to a green fuel
formulation. In an embodiment, the fifth hydrocarbon stream
comprises equal to or greater than about 99 weight percent
isoparaffins having from about 11 to about 13 carbon atoms.
[0054] In certain embodiments, the first hydrocarbon stream may be
further combined with oil for use of the green fuel in 2-cycle
engines. In an embodiment, the type of oil and ratio of green fuel
combined with oil is according to engine manufacturer
specifications. In another embodiment, the ratio of green fuel to
oil is about 40:1. An example of a suitable oil for mixing with the
green fuel is the Synjex.RTM. 2-Cycle Motor Oil manufactured by
ConocoPhillips Company. Table 17 presents typical physical
properties of a suitable 2-cycle oil. TABLE-US-00018 TABLE 17
Example Motor Oil for Mixing with Green Fuel Typical Properties
Density, g/cm.sup.3 @ 15.6.degree. C. (60.degree. F.) 0.948 Color,
Visual Purple Flash Point (COC), .degree. C. (.degree. F.) 112
(234) Pour Point, .degree. C. (.degree. F.) -48 (-54) Viscosity, cP
@ -40.degree. C. (Brookfield) 39,000 cSt @ 40.degree. C. 58.1 cSt @
100.degree. C. 9.2 SUS @ 100.degree. F. 297 SUS @ 210.degree. F.
57.2 Viscosity Index 139 Sulfated Ash, ASTM D874, wt. % Nil
[0055] Further embodiments of methods may comprise selecting a
first hydrocarbon stream comprising equal to or greater than about
99 liquid volume percent saturated hydrocarbons having from about 4
to about 9 carbon atoms; combining the first hydrocarbon stream
with a second hydrocarbon stream comprising at least about 50
weight percent naphthenes; and formulating a fuel from a mixture
comprising the first hydrocarbon stream and second hydrocarbon
stream, wherein the fuel comprises a specific gravity according to
ASTM D-4052 effective for use in 2-cycle and 4-cycle off-road
engines.
[0056] The methods of combining the hydrocarbon streams and
ingredients described above may be carried out in any number of
sequences. Further, any number of combinations of the methods,
hydrocarbon streams, and ingredients may be employed to achieve the
desired characteristics of the green fuels.
[0057] Embodiments disclosed herein also include a method
comprising packaging the fuel described herein in units of less
than or equal to about 10 gallons, alternatively less than or equal
to about 5 gallons, and selling the fuel for use in off-road
engines. Such engines may comprise any 2-cycle or 4-cycle off-road
engine, such as engines employed in snowmobiles, jet skis,
watercraft, portable generators, 2-wheel all-terrain vehicles,
3-wheel all-terrain vehicles, 4-wheel all-terrain vehicles, dirt
bikes, outboard boat motors, chain saws, wood chippers, mower
tractors, push mowers, weed trimmers, blowers, power washers, brush
shredders, line trimmers, chain saws, tillers, and the like. In an
embodiment, the off-road engines are small off-road engines having
a displacement of equal to or less than about 1 liter,
alternatively equal to or less than about 0.75 liter, alternatively
equal to or less than about 0.5 liter, or alternatively equal to or
less than about 0.25 liter. Such engines are filled with the green
fuel as disclosed herein and operated according to manufacturer's
instructions. In an embodiment, the prepackaged fuel further
comprises 2-cycle engine oil co-packaged therewith or pre-mixed
with the fuel in one or more green ratios (e.g., prepackaged 32:1,
prepackaged 40:1, etc.). In an embodiment, the method of packaging
and selling comprises selling the fuel in retail stores, for
example in racks or cages placed in a safe location.
EXAMPLES
[0058] The invention having been generally described, the following
examples are given as particular embodiments of the invention and
to demonstrate the practice and advantages thereof. It is
understood that the examples are given by way of illustration and
are not intended to limit the specification or the claims that
follow in any manner. Particular data for the following examples
were derived from the Developmental Fuels Emissions Evaluation,
Final Report, performed by Southwest Research Institute; SwRI
Project No. 03.10434; 28 May 2004.
[0059] The following examples, 1-2, compare various characteristics
of an exemplary green fuel, oxygenated green fuel, and standard
reference fuel. Table 18a shows the distributions of various
constituents and compounds in an exemplary green fuel, oxygenated
green fuel, and reference fuel, as were employed in examples 1-2.
Table 18b shows various identifying properties for an exemplary
green fuel, oxygenated green fuel, and reference fuel, as were
employed in examples 1-2. Table 18c shows manufacturer
specifications for each engine. The 4-stroke engines were operated
with SAE 30W oil. A synthetic oil was blended with the fuels at the
engine manufacturer's recommended 40:1 ratio for the 2-stroke
engine. TABLE-US-00019 TABLE 18a Example Distributions of Various
Constituents and Compounds in a Green Fuel, Oxygenated Green Fuel,
and Reference Fuel Oxygenate Green Green Fuel Fuel Reference GROUP
CARBON# % MOL % MOL % MOL Aromatics 6 -- -- 1.029 7 -- -- 7.102 8
-- -- 10.163 9 -- -- 4.862 10 -- -- 2.311 11 -- -- 0.402 12 -- --
0.365 Paraffin 3 -- -- 0.038 4 4.271 5.566 8.405 5 0.78 0.346 1.413
6 0.026 0.018 0.983 7 -- 2.752 2.99 8 -- -- 0.665 9 1.149 1.043
0.228 10 0.02 0.018 0.079 11 0.005 0.004 0.044 12 -- -- 0.02
Isoparaffins 4 0.073 0.106 0.333 5 10.937 10.218 7.98 6 15.072
8.696 5.424 7 18.087 20.133 9.528 8 25.593 19.877 13.339 9 3.782
3.519 2.292 10 5.473 5.069 0.747 11 0.281 0.258 0.226 12 0.011
0.012 0.133 13 -- -- 0.021 Naphthenes 5 8.342 3.047 0.121 6 --
0.006 1.242 7 -- 0.328 1.969 8 0.379 0.366 1.624 9 1.756 1.63 0.607
10 1.224 1.146 0.135 11 0.273 0.252 0.051 12 -- -- 0.005 Olefins 4
-- 0.006 0.411 5 0.007 0.04 4.37 6 3.095 7 -- 0.464 2.159 8 -- --
0.452 9 0.034 0.035 0.267 10 0.038 0.031 0.029 Oxygenates 6 --
12.374 --
[0060] TABLE-US-00020 TABLE 18b Fuel Properties according to ASTM
D-5291 and D-4052 Fuel ID Reference Fuel Oxygenated Green Fuel
Green Fuel Carbon, % 86.37 82.40 84.00 Hydrogen, % 13.83 15.64
16.02 Oxygen, % -- 1.96 -- (by difference) API Gravity 61.0 70.2
71.4 Density, g/ml 0.7349 0.7013 0.6972 Specific 0.7352 0.7015
0.6974 Gravity
[0061] TABLE-US-00021 TABLE 18c Test Engines Engine Type 2-Stroke
Handheld 4-Stroke Side Valve 4-Stroke Overhead Valve Manufacturer
Troy Built Briggs and Stratton Honda Engine Family 4MTDS.0314RA:EM
3BSXS.1901VH 2HNXS.1611.AK Displacement 31 cc (1.9 in.sup.3) 188 cc
(11.5 in.sup.3) 160 cc (9.7 in.sup.3) Certification 2004 EPA Phase
2 2006 California and EPA 2007 EPA Phase 2 and Phase 2 2006 CARB
Tier II
Example 1
[0062] Tables 19a through 19c compare emissions of selected toxic
compounds from a green fuel, oxygenated green fuel, and reference
standard fuel during operation of the tree off-road engines
identified in Table 18c. Data were colledcted in accordance with 6
Mode California Air Resources Board Small Off-Road Engine test.
Table 19a shows emissions data when operating the side-valve,
4-stroke engine, Table 19b shows emissions data when operating the
overhead valve, 4-stroke engine, and Table 19c shows emissions data
when operating the 2-stroke engine. The data in Tables 19a, 19b,
and 19c show that emissions of certain compounds from the green
fuel and oxygenated green fuel were generally lower compared to the
reference standard fuel for all three engine types. In particular,
the data show the green fuels will reduce aromatic hydrocarbon
emissions by no less than 80 percent. TABLE-US-00022 TABLE 19a
Selected Hydrocarbon Species, Side-Valve, 4-Stroke Engine
Composite, mg/hp-hr Reference Oxygenated Compound/Fuel Fuel Green
Fuel Green Fuel 1,3-BUTADIENE 57 39 72 ETBE <1 333 <1 BENZENE
323 40 64 TOLUENE 514 57 72 ETHYLBENZENE 139 4 3 m-& p-XYLENE
324 12 7 o-XYLENE 104 47 58 BENZALDEHYDE 8 <1 <1
m-/p-TOLUALDEHYDE 10 1 3
[0063] TABLE-US-00023 TABLE 19b Selected Hydrocarbon Species,
Overhead Valve, 4-Stroke Engine Composite, mg/hp-hr Reference
Oxygenated Compound/Fuel Fuel Green Fuel Green Fuel 1,3-BUTADIENE
49 37 49 ETBE <1 210 <1 BENZENE 276 50 33 TOLUENE 536 48 55
ETHYLBENZENE 153 4 1 m-& p-XYLENE 387 9 4 o-XYLENE 125 38 45
BENZALDEHYDE 6 <1 <1 m-/p-TOLUALDEHYDE 5 1 1
[0064] TABLE-US-00024 TABLE 19c Selected Hydrocarbon Species,
2-Stroke Engine Composite, mg/hp-hr Reference Oxygenated
Compound/Fuel Fuel Green Fuel Green Fuel 1,3-BUTADIENE 456 266 347
ETBE <1 10883 <1 BENZENE 1046 181 76 TOLUENE 7577 441 2061
ETHYLBENZENE 2518 67 48 m-& p-XYLENE 5448 226 120 o-XYLENE 1950
1046 1241 BENZALDEHYDE 50 3 1 m-/p-TOLUALDEHYDE 96 3 7
Example 2
[0065] Table 20 expresses the emissions data for selected compounds
in terms of the percent change in emissions compared to the
reference fuel. The columns of emissions data under each fuel
represent emissions from different engine types, plus the average
emissions for each fuel across all engine types. The engine types
were `side-valve, 4-stroke` (SV4S), `overhead-valve, 4-stroke`
(OHV4S), and `2-stroke` (2S). Particulate matter emissions data was
not available for 4-stroke engines. Across fuels and engine types,
the reduction in emissions of benzene ranged from 82.0 to 92.7
percent; the reduction in emissions of 1,3-butadiene ranged from
0.8 to 41.7. TABLE-US-00025 TABLE 20 Percent Change in Emissions
Compared to Reference Fuel Oxygenated Green Fuel Green Fuel Engine
Type SV4S OHV4S 2S Average SV4S OHV4S 2S Average Total hydrocarbons
(THC) -1.9 -6.5 -9.4 -5.9 +9.7 +2.7 +1.3 +4.6 Oxides of Nitrogen
(NO.sub.x) -3.9 +4.7 0 +0.3 -0.6 -13.1 -24.1 -12.6 Carbon monoxide
(CO) -13.0 -13.4 -22.6 -16.3 -10.3 -4.7 +1.3 -4.6 Ozone formation
potential -2.1 -4.4 -29.7 -12.1 +21 +3.0 -18.1 -0.03 Particulate
Matter N/A N/A -28.8 -28.8 N/A N/A -4.7 -4.7
[0066] While preferred embodiments of the invention have been shown
and described, modifications thereof can be made by one skilled in
the art without departing from the spirit and teachings of the
invention. The embodiments and examples described herein are
exemplary only, and are not intended to be limiting. Many
variations and modifications of the invention disclosed herein are
possible and are within the scope of the invention. Use of the term
"optionally" with respect to any element of a claim is intended to
mean that the subject element is required, or alternatively, is not
required. Both alternatives are intended to be within the scope of
the claim. Use of broader terms such as comprises, includes,
having, etc. should be understood to provide support for narrower
terms such as consisting of, consisting essentially of, comprised
substantially of, etc.
[0067] Accordingly, the scope of protection is not limited by the
description set out above but is only limited by the claims which
follow, that scope including all equivalents of the subject matter
of the claims. Each and every claim is incorporated into the
specification as an embodiment of the present invention. Thus, the
claims are a further description and are an addition to the
preferred embodiments of the present invention. The discussion of a
reference in the Description of Related Art is not an admission
that it is prior art to the present invention, especially any
reference that may have a publication date after the priority date
of this application. The disclosures of all patents, patent
applications, and publications cited herein are hereby incorporated
by reference, to the extent that they provide exemplary, procedural
or other details supplementary to those set forth herein.
* * * * *