Biodiesel fuel mixtures

Abstract

Provided herein are biodiesel fuel mixtures having improved properties for reducing NOx emissions as well as total particular matter emissions, CO emissions, and total hydrocarbon emissions.

Description

BACKGROUND

Biodiesel, an alternative diesel fuel created from the esterification of fats and fatty acids, continues to gain significant interest as a renewable energy source. The biodiesel market is expected to reach 6,453 million liters in the U.S. by 2020 and 45,291 million liters globally. See GlobalData, Global Biodiesel Market Analysis and Forecasts to 2020, Accessed May 26, 2012 and Fuel Processing Technology 106 (2013) 526-532. Biodiesel is an attractive alternative fuel source worldwide because it operates in conventional engines, does not require special storage, has less odor offensive exhaust, and has a higher flash point, thereby making it a safer energy source than conventional diesel fuel.

Despite these advantages, a major impediment to the wide-spread committed use of biodiesel has been the observed increase in NO_x emissions. For example, for 100% biodiesel, NO_x emissions can increase by 13% or more. See Ener Conver and Manag, 50, (2009), 14-34. Excessive NOx emission causes smog, ground level ozone, and acid rain. See Journal of Scientific & Industrial Industry Research, Vol. 73, March 2014, 177-180. This is a significant drawback, particularly since governmental agencies continue to impose new legislation on “cleaner air” and mandate higher emission standards for motor vehicles. Thus, a rising concern is that biodiesel may not be able to meet these heightened requirements.

The need therefore remains for biodiesel fuels which do not negatively impact NO_x emission, as well as other criteria pollutants such as particulate matter, total hydrocarbons and carbon monoxide.

SUMMARY

Provided herein are biodiesel fuel mixtures comprising a first biodiesel fuel, a second biodiesel fuel, a base petroleum diesel fuel, and an additive. The disclosed biodiesel fuel mixtures comprise a cetane number of 45 to 70 and have no negative impact on NO_x emissions. Indeed, the disclosed mixtures decrease NO_x emission by 1 to 7%. See e.g., Table 12. The disclosed mixtures also decrease total particular matter emissions, CO emissions, and total hydrocarbon emissions. See e.g., Table 12.

Process for manufacturing the disclosed biodiesel fuel mixtures are also provided.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graphic representation of torque and speed commands for the transient cycle for heavy-duty engines.

FIG. 2 is a schematic of sampling system used for transient emission measurements.

FIG. 3 shows the engine performance maps for screening tests.

FIG. 4 shows the engine performance maps for screening tests at 3000 ppm additive.

FIG. 5 shows the engine performance maps for screening tests at 2000 ppm additive.

FIG. 6 illustrates additive concentration vs. NO_x results.

FIG. 7 shows a comparison of B20 blends.

FIG. 8 shows a comparison of B20 blends with 3000 ppm A1

FIG. 9 shows a comparison of B20 blends with 3000 ppm additive.

DETAILED DESCRIPTION

In a first embodiment, provided herein are biodiesel fuel mixtures comprising a first biodiesel fuel, a second biodiesel fuel, a base petroleum diesel fuel, and an additive, wherein the biodiesel fuel mixture has a cetane number of 45 to 70.

In a second embodiment, provided herein are biodiesel fuel mixtures comprising 12-15 wt. % of a first biodiesel fuel, 6-8 wt. % of a second biodiesel fuel, 79-81 wt. % of a base petroleum diesel fuel, and an additive, wherein the biodiesel fuel mixture has a cetane number of 45 to 70.

In a third embodiment, provided herein are biodiesel fuel mixtures comprising 13 wt. % of a first biodiesel fuel, 7 wt. % of a second biodiesel fuel, 80 wt. % of a base petroleum diesel fuel, and from 100 to 3500 ppm of an additive, wherein the biodiesel fuel mixture has a cetane number of 45 to 70.

1. Definitions

The term “biodiesel” means a fuel derived from vegetable oils or animal fats. Biodiesel includes fuels comprising mono-alkyl esters of long-chain fatty acids derived from the transesterification of fats obtained from vegetable oils or other fatty acids such as animal fats or waste cooking oils as well as fuel resulting from hydrotreating vegetable oils, animal fats or mono-alkyl esters of long-chain fatty acids. In one aspect, the biodiesel used herein comprises fatty acid methyl esters (FAMEs) derived from the transesterification of vegetable oil with methanol.

“Petroleum diesel fuel” and “base petroleum diesel fuel” are used interchangeably and refer to a combustible petroleum distillate used as fuel for diesel engines. Petroleum diesel fuel is typically formed from the fractional distillation of crude oil between 200° C. and 350° C. at atmospheric pressure, resulting in a mixture of carbon chains comprising between 8 and 21 carbon atoms per molecule.

The term “no negative impact” as in, wherein the mixture has no negative impact on NO_x emissions, means that there is no statistically significant increase in the amount of NO_x emission using the disclosed biodiesel fuel mixture when compared to petroleum diesel fuel in the same engine. Statistical significance is based from the known one-sided Student's t-statistics as set for in Snedecor and Cochran, Statistical Methods (7^th edition). Pg 91, Iowa State University Press, 1980, e.g., a cut-off value of 0.5 or less.

2. Fuel Mixtures

In a fourth embodiment, the biodiesel fuel mixtures described herein have a cetane number of 45 to 65, wherein the remaining features are as described above in the first, second, or third embodiment. Alternatively, the biodiesel fuel mixtures described herein have a cetane number of 45 to 60, 45 to 55, 55 to 65, 50 to 60, 48 to 51, or 58 to 60, wherein the remaining features are as described above in the first, second, or third embodiment.

In a fifth embodiment, the biodiesel fuel mixtures described herein comprise 25% or less of aromatics by volume, wherein the remaining features are as described above in the first, second, third, or fourth embodiment. Alternatively, the biodiesel fuel mixture described herein comprise 20% or less of aromatics by volume, 15% or less of aromatics by volume, 12% or less of aromatics by volume, 10% or less of aromatics by volume, or 20% to 25% aromatics by volume, wherein the remaining features are as described above in the first, second, third, or fourth embodiment.

In a sixth embodiment, the biodiesel fuel mixtures described herein comprise less than 7% polycyclic aromatics by weight, wherein the remaining features are as described above in the first, second, third, fourth, or fifth embodiment. Alternatively, the biodiesel fuel mixtures described herein comprise less than 5% polycyclic aromatics by weight or 4.5% to 5.5% polycyclic aromatics by weight, wherein the remaining features are as described above in the first, second, third, fourth, or fifth embodiment.

In a seventh embodiment, the weight ratio of total aromatics to polycyclic aromatics in the biodiesel fuel mixtures described herein is 5:1, wherein the remaining features are as described above in the first, second, third, fourth, fifth, or sixth embodiment. Alternatively, the weight ratio of total aromatics to polycyclic aromatics in the biodiesel fuel mixtures described herein is 4:1, 3:1, or 2:1, wherein the remaining features are as described above in the first, second, third, fourth, fifth, or sixth embodiment.

In an eighth embodiment, the sulfur content in the biodiesel fuel mixtures described herein is less than 15 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, or seventh embodiment. Alternatively, the sulfur content in the biodiesel fuel mixtures described herein is less than 10 ppm, less than 5 ppm, less than 1.0 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, or seventh embodiment.

In a ninth embodiment, the nitrogen content in the biodiesel fuel mixtures described herein is from 0 to about 800 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, or eighth embodiment. 200 ppm or higher, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, or eighth embodiment. Alternatively, the nitrogen content in the biodiesel fuel mixtures described herein is from 50 ppm to about 600 ppm, from about 100 to about 400 ppm, from about 200 to about 800 ppm, from about 10 to about 600 ppm, and from about 250 to about 300 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, or eighth embodiment.

In a tenth embodiment, the fatty acid methyl ester content in the biodiesel fuel mixtures described herein is 15 to 25% or 19 to 21%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, or ninth embodiment.

In an eleventh embodiment, the viscosity at 40° C. in the biodiesel fuel mixtures described herein is 1.9 to 4.1 centistokes, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, or tenth embodiment.

In a twelfth embodiment, the additive in the biodiesel fuel mixtures described herein is present in an amount of 500, 1000, 1500, 2000, 2500, 3000, 3300, 4000, 5000, 6000, 7000, 8000, 9000 or 10,000 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, or eleventh embodiment. Alternatively, the additive is present in an amount of 3300 ppm or 3000 ppm, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, or eleventh embodiment.

In a thirteenth embodiment, the additive in the biodiesel fuel mixtures described herein is selected from an amine-based antioxidant, a phenol-based antioxidant, or a nitrated alkyl-based antioxidant, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twelfth embodiment. Alternatively, the additive is selected from 2-ethylhexyl nitrate (2-EHN); di-tert-butyl peroxide (DTBP); tertiary butylhydroquinone (TBHQ); N,N-di-sec-butyl-1,4-phenylenediamine (DTBP), N,N′-diphenyl-1,4-phenylenediamine (DPPD); and N-phenyl-1,4-phenylenediamine (NPPD), wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twelfth embodiment. In another alternative, the additive is 2-ethylhexyl nitrate, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twelfth embodiment.

In a fourteenth embodiment, the biodiesel fuel mixtures described herein have no negative impact on NO_x emissions, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, or thirteenth embodiment.

In a fifteenth embodiment, the biodiesel fuel mixtures described herein decrease NO_x emissions of an engine by 1 to 7%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, or fourteenth embodiment. Alternatively, the biodiesel fuel mixtures described herein decrease NO_x emissions of an engine by 2 to 7%; by 3 to 7%; or by 5 to 7%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, or fourteenth embodiment. In one alternative, the biodiesel fuel mixtures described herein comprise NOx emissions equivalent to those of a reference fuel having the following specifications: sulfur (15 ppm maximum), aromatics (10 vol % maximum), polycyclic aromatics (10 wt % maximum), nitrogen (10 ppm maximum), unadditized cetane number (48 minimum), API gravity (33-39), flash point (130° F. minimum), viscosity @ 40° C., cSt (2.0-4.12), IBP (340 to 420° F.), 10% (400 to 490° F.), 50% (470 to 560° F.), 90% (550 to 610° F.), and EP (580 to 660° F.).

In a sixteenth embodiment, the biodiesel fuel mixtures described herein decrease total particular matter emissions of an engine by 20 to 25%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, fourteenth, or fifteenth embodiment.

In a seventeenth embodiment, the biodiesel fuel mixtures described herein decrease CO emissions of an engine by 15 to 25%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, fourteenth, fifteenth, or sixteenth embodiment.

In an eighteenth embodiment, the biodiesel fuel mixtures described herein decrease total hydrocarbon emissions of an engine by 15 to 25%, wherein the remaining features are as described above in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, fourteenth, fifteenth, sixteenth, or seventeenth embodiment.

In a nineteenth embodiment, the engine used to test the properties of the biodiesel fuel mixtures described herein is a diesel engine such as a Detroit Diesel Corporation Series 60 heavy duty diesel engine or a Cummins ISM 370 diesel engine.

In a twentieth embodiment, the biodiesel fuel mixtures, and accompanying properties and features are as described below in the exemplification section.

EXEMPLIFICATION

The following starting fuels and additives were blended at various concentrations. Table 1 provides codes for the six additives and Table 2 lists the fuel codes corresponding to each fuel blend and the concentrations.

TABLE 1
	Component %
	Additive Code	2-EHN	DTBP	PDA
	A1, A7	100	0	0
	A2	91	0	9
	A3	91	9	0
	A4	0	100	0
	A5	82	9	9
	A6	0	0	100

TABLE 2
	Concentration, %a
Fuel	Base
Code	Fuel	Biodiesel 1	Biodiesel 2	Biodiesel 3	Additive/Conc.
F1	—	100	—	—	—
F2	—	—	100	—	—
F3	—	—	—	100	—
F4	100	—	—	—	—
F5	80	13	7	—	—
F6	80	—	—	20	—
F7	80	—	—	20	3000
F8	80	13	7	—	3000
F9	80	13	7	—	1000
F10	80	13	7	—	2000
F11	80	13	7	—	1500
F12	80	13	7	—	3300b
F13	80	13	7	—	3300c
F14	80	13	7	—	2500
aConcentrations for fuel in percentage, concentration for additive in ppm, additive A1 1000 unless indicated
bAdditive A3
cAdditive A2

Fuel blends were tested using procedures similar to the one outlined in Title 13 California Code of Regulations Section 2882 “Aromatic Hydrocarbon Content of Diesel Fuel.” The actual screening plan is shown in Table 3. For screening, Alternative 3 was the Title 13 protocol selected. For the first two days of testing, duplicate tests with only a single “prep” were used to quickly move through a large number of fuels. After the first day of testing, the B100 blend with F1 (35 percent) and F2 (65 percent) was selected as the B100 for all subsequent testing. On the final two days of testing, the Alternative 3 procedure was followed to screen a 3000 ppm and 2000 ppm additive, respectively. The test results are reported below in Table 3.

The heavy-duty EPA transient cycle is described by means of percent of maximum torque and percent of rated speed for each one-second interval over a test cycle of 1199 seconds duration. To generate a transient cycle, an engine's full power curve is obtained from an engine speed below curb idle speed to maximum no-load engine speed. Data from this “power curve,” or engine map, are used with the specified speed and load percentages to form a transient cycle. A graphic presentation of the speed and torque commands which constitute a transient cycle is given in FIG. 1 for illustration purposes.

In general, a transient test consists of a cold-start transient cycle and a hot-start transient cycle. The same engine command cycle is used in both cases. For the cold-start, the diesel engine was operated over a “prep” cycle, and then allowed to stand overnight in an ambient soak at a temperature between 68° F. and 86° F. The cold-start transient cycle begins when the engine is cranked for cold start-up. Upon completion of the cold-start transient cycle, the engine is stopped and allowed to stand for 20 minutes. After this hot-soak period, a hot-start cycle begins with engine cranking. In order to determine how well the engine follows the transient command cycle, engine performance was compared to engine command, and several statistics were computed. These computed statistics must be within tolerances specified in the CFR. In addition to statistical parameters, the cycle work actually produced should be between 5 percent above and 15 percent below the work requested by the command cycle. Emissions measurements included total hydrocarbon (THC), carbon monoxide (CO), oxides of nitrogen (NO), carbon dioxide (CO₂), and total particulate matter (PM).

TABLE 3
Step Description
1    Install engine. Perform emission instrument calibrations as
     required. Calibrate torquemeter and check signal conditioning
     systems. Validate CVS gaseous and particulate sampling systems
     using propane recovery techniques
2    Change oil and filters. Operate engine for 5 hours with CARB
     equivalent fuel to break-in the oil, Check engine condition using
     in-house, low sulfur emissions type fuel, and note fault codes
     if any. Bring engine oil level to “full”.
3    Perform fuel change procedure to operate on Fuel R (F4). Change
     filter, purge fuel supply, etc.
4    Warm up engine, and operate at rated speed and load, then check
     performance.
5    Conduct transient “full-throttle” torque map from low- to high-idle.
     Compute and store resulting transient command cycle.
6    Run a 20-minute practice or conditioning transient cycle, and
     adjust dynamometer controls to meet statistical limits for transient
     cycle operation.
7    Soak the engine for 20-minutes. Run three hot-start transient tests
     with a 20-minute soak between each. For each individual hot-start
     test, determine THC, CO, NOx, CO2, and PM.
8    Change fuel to F5. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
9    Change fuel to F6. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
10   Change fuel to F7. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
11   Change fuel to F8. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
12   Change fuel to F9. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
13   Change fuel to F10. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
14   Change fuel to F11. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
15   Change fuel to F4. Repeat Steps 6 and 7. Soak the engine for 20-
     minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
16   Change fuel to F8. Repeat Steps 6 and 7 except that the fuel filters
     should be dumped, and the engine should be run for 20 minutes at
     rated speed and load prior to Step 7. Soak the engine for
     20-minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
17   Change fuel to F13. Repeat Steps 6 and 7 except that the fuel
     filters should be dumped, and the engine should be run for 20
     minutes at rated speed and load prior to Step 7. Soak the engine
     for 20-minutes. Run two hot-start transient tests with a 20-minute
     soak between each. For each individual hot-start test, determine
     THC, CO, NOx, CO2, and PM.
18   Change fuel to F12. Repeat Steps 6 and 7 except that the fuel
     filters should be dumped, and the engine should be run for 20
     minutes at rated speed and load prior to Step 7. Soak the engine
     for 20-minutes. Run two hot-start transient tests with a 20-minute
     soak between each. For each individual hot-start test, determine
     THC, CO, NOx, CO2, and PM.
19   Change fuel to F5. Repeat Steps 6 and 7 except that the fuel filters
     should be dumped, and the engine should be run for 20 minutes at
     rated speed and load prior to Step 7. Soak the engine for
     20-minutes. Run two hot-start transient tests with a 20-minute soak
     between each. For each individual hot-start test, determine THC,
     CO, NOx, CO2, and PM.
20   Change fuel to F14. Repeat Steps 6 and 7 except that the fuel
     filters should be dumped, and the engine should be run for 20
     minutes at rated speed and load prior to Step 7. Soak the engine
     for 20-minutes. Run two hot-start transient tests with a 20-minute
     soak between each. For each individual hot-start test, determine
     THC, CO, NOx, CO2, and PM.
21   Change fuel to F4. Repeat Steps 4 through 8.
22   Change fuel to F8. Repeat Steps 4 through 8.
23   Change fuel to F4. Repeat Steps 4 through 8.
24   Change fuel to F10. Repeat Steps 4 through 8.

For this screening work, a 1991 DDC Series 60 heavy-duty diesel engine was mounted in a transient-capable test cell. This engine had an inline, six cylinder configuration rated for 365 hp at 1800 rpm. It was turbocharged and used a laboratory water-to-air heat exchanger for a charge air intercooler. Table 4 lists the engine specifications and features.

TABLE 4
Engine Parameter                 Comment
Make                             Detroit Diesel
Model                            Series 60, 6067GU60
Engine Displacement and Configuration 12.7 L, I-6
Emission Family                  MDD12.7FZAK
Rated Power                      365 bhp at 1800 rmp
Electronic Control Module        DDEC-II
Aspiration                       Turbocharged

For emission testing, the exhaust was routed to a full flow constant volume sampler (CVS) that utilized a positive displacement pump (PDP), as illustrated in FIG. 2. Total flow in the tunnel was maintained at a nominal flow rate of about 2000 SCFM. Sample zone probes were connected to the main tunnel. These probes were used to collect samples for total particulate (PM) and for the gaseous emissions: NON, THC, CO, and CO₂. The NO_x was analyzed using a chemiluminescent (CL) analyzer, the THC used a flame ionization detector (FID), and CO and CO₂ was performed using separate non-dispersive infrared (NDIR) detectors. Probes for background gas measurement were connected downstream of the dilution air filter pack, but upstream of the mixing section. Background concentrations were determined for all emissions, and the tunnel THC background was also determined before and after each test. This engine produced emission results less than or equivalent to the standards for that model year. Table 5 compares the 1991 emission standards, the average reference fuel emission results, and the percent of standard for these tests. The engine did not exceed 110 percent of the applicable emission standards for a 1991 model engine.

TABLE 5
	Transient Emission, G/HP-HR
	Test Number	THC	CO	NOx	PM
	1991 Standard	1.3	15.5	5.0	0.25
	Reference Fuel	0.1	2.4	4.5	0.19
	% of Standard	7	16	90	75

FIG. 3 shows a graphical representation of the torque map data for the screening tests, and FIGS. 4 and 5 show the torque map data for the tests with 3000 ppm and 2000 ppm of the additive, respectively. Table 6 gives all of the emission results for THC, CO, NO_x, PM, and brake specific fuel consumption (BSFC) obtained for each of the tests. This table groups the tests by fuels and additives rather than in the order that the tests were performed. The average, standard deviation, and coefficient of variation for each set of hot-start transient tests are also included for each fuel. FIG. 6 shows the NOx emissions versus additive concentration with trend lines for a possible shift in baseline.

TABLE 6
FUEL	TRANSIENT EMISSIONS, g/hp-hr	BSFC,	WORK,
CODE	RUN #	CO2	CO	THC	NOX	PM	lb/hp-hr	hp-hr
F4	1308	531.7	2.5	0.10	4.521	0.177	0.371	24.61
	1309	531.4	2.5	0.10	4.501	0.194	0.371	24.60
	1310	531.2	2.5	0.10	4.506	0.192	0.371	24.60
	Average	531.4	2.5	0.10	4.509	0.187	0.371	24.61
	Std. Dev.	0.247	0.0	0.00	0.010	0.010	0.000	0.002
F4	1340	529.7	2.5	0.09	4.475	0.189	0.370	24.60
	1341	530.0	2.5	0.09	4.487	0.185	0.370	24.61
	Average	529.9	2.5	0.09	4.481	0.187	0.370	24.60
	Std. Dev.	0.232	0.0	0.00	0.008	0.003	0.000	0.002
F4	1362	531.8	2.4	0.08	4.553	0.180	0.371	24.49
	1363	532.8	2.4	0.08	4.560	0.180	0.371	24.49
	1364	533.4	2.4	0.08	4.565	0.184	0.372	24.49
	Average	532.7	2.4	0.08	4.559	0.181	0.372	24.49
	Std. Dev.	0.808	0.0	0.00	0.006	0.002	0.000	0.003
F4	1370	529.4	2.5	0.09	4.463	0.184	0.370	24.69
	1371	529.6	2.4	0.09	4.474	0.180	0.370	24.69
	1372	530.7	2.5	0.09	4.483	0.179	0.371	24.69
	Average	530.2	2.5	0.09	4.478	0.180	0.370	24.69
	Std. Dev.	0.759	0.1	0.00	0.006	0.001	0.001	0.001
F5	1312	532.0	2.3	0.10	4.601	0.162	0.380	24.57
	1213	532.1	2.2	0.10	4.607	0.154	0.380	24.59
	Average	532.1	2.3	0.10	4.604	0.158	0.380	24.58
	Std. Dev.	0.086	0.1	0.00	0.004	0.005	0.000	0.011
F5	1355	531.0	2.2	0.08	4.595	0.151	0.379	24.55
	1356	533.1	2.2	0.08	4.630	0.146	0.381	24.56
	Average	532.0	2.2	0.08	4.613	0.148	0.380	24.55
	Std. Dev.	1.476	0.0	0.00	0.025	0.003	0.001	0.01
F6	1315	532.1	2.2	0.09	4.622	0.157	0.380	24.57
	1316	532.1	2.2	0.09	4.620	0.158	0.380	24.58
	Average	532.1	2.2	0.09	4.621	0.157	0.380	24.58
	Std. Dev.	0.026	0.0	0.00	0.001	0.001	0.000	0.008
F7	1318	531.3	2.0	0.08	4.420	0.154	0.379	24.61
	1319	530.8	2.0	0.08	4.416	0.149	0.379	24.60
	Average	531.0	2.0	0.08	4.418	0.151	0.379	24.61
	Std. Dev.	0.350	0.0	0.00	0.003	0.004	0.000	0.004
F9	1324	526.1	2.2	0.08	4.390	0.150	0.376	24.63
	1325	527.6	2.2	0.08	4.403	0.149	0.377	24.63
	Average	526.8	2.2	0.08	4.397	0.149	0.376	24.63
	Std. Dev.	1.080	0.0	0.00	0.009	0.000	0.001	0.00
F11	1330	529.4	2.1	0.08	4.419	0.151	0.378	24.60
	1331	529.0	2.0	0.08	4.419	0.146	0.378	24.60
	Average	529.2	2.1	0.08	4.419	0.148	0.378	24.60
	Std. Dev.	0.291	0.1	0.00	0.000	0.004	0.000	0.004
F10	1327	529.2	2.0	0.08	4.405	0.150	0.378	24.60
	1328	529.5	2.1	0.08	4.401	0.144	0.378	24.60
	Average	529.3	2.1	0.08	4.403	0.147	0.378	24.60
	Std. Dev.	0.206	0.1	0.00	0.002	0.004	0.000	0.004
F10	1374	533.2	2.1	0.07	4.449	0.142	0.381	24.68
	1375	533.9	2.0	0.07	4.459	0.147	0.381	24.69
	1376	533.7	2.1	0.07	4.459	0.149	0.381	24.70
	Average	533.6	2.1	0.07	4.455	0.146	0.381	24.69
	Std. Dev.	0.362	0.1	0.00	0.006	0.004	0.000	0.012
F14	1358	534.7	2.2	0.07	4.483	0.148	0.382	24.53
	1359	534.5	2.1	0.07	4.485	0.146	0.382	24.55
	Average	534.6	2.1	0.07	4.484	0.147	0.382	24.54
	Std. Dev.	0.104	0.0	0.00	0.001	0.001	0.000	0.012
F8	1321	528.7	2.0	0.08	4.356	0.143	0.377	24.63
	1322	529.9	2.0	0.07	4.337	0.143	0.375	24.64
	Average	529.3	2.0	0.08	4.347	0.143	0.376	24.64
	Std. Dev.	0.865	0.0	0.00	0.013	0.000	0.001	0.009
F8	1346	528.7	2.0	0.08	4.386	0.142	0.378	24.57
	1347	529.9	2.0	0.07	4.402	0.143	0.378	24.56
	Average	529.3	2.0	0.08	4.394	0.142	0.378	24.56
	Std. Dev.	0.865	0.0	0.00	0.012	0.001	0.001	0.009
F8	1366	535.1	2.1	0.07	4.473	0.148	0.382	24.46
	1367	534.8	2.0	0.07	4.480	0.147	0.382	24.47
	1368	534.8	2.1	0.07	4.472	0.149	0.382	24.48
	Average	534.9	2.1	0.07	4.475	0.148	0.382	24.47
	Std. Dev.	0.147	0.1	0.00	0.004	0.001	0.000	0.006
F13	1349	531.7	2.0	0.07	4.409	0.150	0.380	24.54
A2	1350	532.5	2.0	0.07	4.415	0.152	0.380	24.55
	Average	532.1	2.0	0.07	4.412	0.151	0.380	24.54
	Std. Dev.	0.539	0.0	0.00	0.004	0.002	0.000	0.01
F12	1352	528.0	2.1	0.07	4.389	0.152	0.377	24.58
A2	1353	529.2	2.1	0.07	4.411	0.147	0.378	24.59
	Average	528.6	2.1	0.07	4.400	0.149	0.378	24.59
	Std. Dev.	0.0805	0.0	0.00	0.016	0.004	0.001	0.01

Two different biodiesels were used. F3 was blended at a concentration of 20 percent biodiesel in the base fuel, F4 to make F6. The other B20 (20 percent biodiesel and 80 percent diesel) blend was a combination of F1 at a concentration of 35 percent and F2 at a concentration of 65 percent. See Table 2. The blend of these two biodiesels was then mixed with the base fuel to make a second B20 blend (F5). FIG. 7 compares the emission results for both biodiesels when blended at a concentration of 20 percent biodiesel. F5 produced slightly less NO_x than the single component biodiesel blend.

The two B20 blends were then mixed with the additive (A1) at a concentration of 3000 ppm. F8 was the B20 blend with a combination of F1 at a concentration of 35 percent and F2 at a concentration of 65 percent, and F7 was the B20 blend with F6 (See Table 2). FIG. 8 compares the emission results for the two B20 blends with the additive at 3000 ppm. F8 produced slightly less NO_x than the single component biodiesel blend.

Two additional additives were blended with F8 at a concentration of 3300 ppm. The two additives were A2 and A3. The fuel codes were F13 and F12, respectively. FIG. 9 compares the emission results for these two additive blends.

Tables 7 and 8 show the statistical approach for comparing the emission results with additive A7 at 3000 ppm and 2000 ppm, respectively. With this approach, the average emissions from the three (3) individual tests with the candidate fuel, Fuel C (Xc), were compared to the average emission results for three (3) individual tests with the reference fuel, Fuel R (XR), by using the one-sided t distribution. The average term for the reference fuel for each emission was adjusted by the tolerance, (1 percent of the average for NOx and 2 percent of the average for CO and PM) and by a value that included: tolerance, δ and pooled standard deviation, S_p.

Square root of two divided by the number of tests, n, for both reference plus candidate (in this case, n=14, to represent the potential result if the entire seven day test protocol was performed) One-sided upper percentage point oft distribution with a=0.15 and 2n−2 degrees of freedom. The equation for this comparison is X_C<X_R+δ−(S_p×√2/η×t(a, 2n−2)). See CCR Title 13, Chapter 5—Standards for Motor Vehicle Fuels, Article 3—Specifications for Alternative Motor Vehicle Fuels. Values presented in Table 7 and 8 were based on a spreadsheet calculation. If the average for the candidate fuel is less than the adjusted average for the reference fuel, then the candidate fuel is comparable or better than the reference fuel.

TABLE 7
	Statistical Criteria	NOx	CO	PM
	Number of Test	14	14	14
	Points, na
	C Average, Xcb	4.475	2.081	0.148
	R Average, XRb	4.559	2.364	0.181
	Tolerance Level, δc	0.046	0.047	0.004
	Pooled std. Dev., Spb	0.005	0.048	0.002
	Sqrt of 2/n	0.378	0.378	0.378
	Student's t, td	1.058	1.058	1.058
	Adjusted R Average,	4.603	2.392	0.184
	Adj. XRb,e
	Is Xc < Adj. XR	Yes	Yes	Yes
	Percent Reduction, r	2.8	13.0	19.7
aFor alternative 4, n = number of tests (plus reference candidate)
bUnits are in g/bhp-hr
cTolerance level is 1 percent for NOx and 2 percent for CO and PM
One-sided student's t for 2n − 2 degrees of freedom and significance level of 0.15
Adj. XR = XR + δ − (Sp × √2/η × t(a, 2n − 2)) where t(a, 2n − 2) is 1.055

TABLE 8
	Statistical Criteria	NOx	CO	PM
	Number of Test	14	14	14
	Points, na
	C Average, Xcb	4.455	2.090	0.146
	R Average, XRb	4.473	2.475	0.181
	Tolerance Level, δc	0.045	0.050	0.004
	Pooled std. Dev., Spb	0.008	0.072	0.003
	Sqrt of 2/n	0.378	0.378	0.378
	Student's t, td	1.058	1.058	1.058
	Adjusted R Average,	4.515	2.496	0.183
	Adj. XRb,e
	Is Xc < Adj. XR	Yes	Yes	Yes
	Percent Reduction, r	1.3	16.3	20.4
aFor alternative 4, n = number of tests (plus reference candidate)
bUnits are in g/bhp-hr
cTolerance level is 1 percent for NOx and 2 percent for CO and PM
One-sided student's t for 2n − 2 degrees of freedom and significance level of 0.15
Adj. XR = XR + δ − (Sp × √2/η × t(a, 2n − 2)) where t(a, 2n − 2) is 1.055

F5 was used in a further blend as follows.

120 gallons of F4 base fuel used as the untreated diesel blend stock were transferred into a clean tote. 30 gallons of F5 and 1703 ml of 2-ethylhexyl nitrate fuel additive were added. The fuel was blended for one hour with an air-actuated stirrer, and a sample was taken for analysis. The fuel properties for the candidate fuel blend are shown in Table 9 together with the properties for base fuel F4. For the fatty acid methyl ester (FAME), the analysis showed that the concentration was 19.8 percent by volume. The resulting treated candidate fuel, Fuel C, was then identified as F15.

TABLE 9
F4 Base Fuel	Value	F15 Candidate Fuel	Value
Sulfur, ppm	0.9	Sulfur, ppm	1.56
Nitrogen, ppm	1.7	Nitrogen, ppm	284.4
Cetane number	49.3	Cetane number	59.1
API Gravity	35.8	API Gravity	34.4
Flash Point, ° F.	197.5 (91.8)	Flash Point	190 (88)
(° C.)
Viscosity @ 40° C.,	3.00	Viscosity @ 40° C.,	3.14
cSt		cSt
IBP, ° F.	400	IBP, ° F.	409
10%, ° F.	451	10%, ° F.	461
50%, ° F.	490	50%, ° F.	521
90%, ° F.	592	90%, ° F.	629
EP, F.	636	EP, F.	644
FAME Content, %	—	FAME Content, %	19.8

Fuel tests were performed utilizing Alternative 3 outlined above and in outlined in Title 13 California Code of Regulations Section 2882. Table 10 provides the testing protocol that was used. F4 is referred to as “Fuel R” for Reference Fuel and F15 is referred to as “Fuel C” for Candidate Fuel.

TABLE 10
Step Description
1    Install engine. Perform emission instrument calibrations as
     required. Calibrate torquemeter and check signal conditioning
     systems. Validate CVS gaseous and particulate sampling systems
     using propane recovery techniques
2    Check engine condition using in-house, low sulfur emissions type
     fuel, and note fault codes if any. Bring engine oil level to “full”.
3    Perform fuel change procedure to operate on Fuel R (F4). Change
     filter, purge fuel supply, etc.
4    Warm up engine, and operate at rated speed and load, then check
     performance.
5    Conduct transient “full-throttle” torque map from low- to high-idle.
     Compute and store resulting transient command cycle.
6    Load dummy sample media, and run a 20-minute practice or
     conditioning transient cycles, and adjust dynamometer controls to
     meet statistical limits for transient cycle operation
7    Soak the engine for 20-minutes. Run three hot-start transient tests
     with a 20-minute soak between each. For each individual hot-start
     test, determine THC, CO, NOx, CO2, and PM.
8    Perform fuel change, and repeat Steps 3 through 7 with Fuel C.
9    On Day 2 of testing, repeat Steps 4 through 9 starting with Fuel C
     and ending with Fuel R.
10   On Day 3 of testing, repeat Steps 4 through 9 starting with Fuel R
     and ending with Fuel C.
11   On Day 4 of testing, repeat Steps 4 through 9 starting with Fuel C
     and ending with Fuel R
12   On Day 5 of testing, repeat Steps 4 through 9 starting with Fuel R
     and ending with Fuel C.
13   On Day 6 of testing, repeat Steps 4 through 9 starting with Fuel C
     and ending with Fuel R.
14   On Day 7 of testing, repeat Steps 4 through 9 starting with Fuel R
     and ending with Fuel C.
15   Summarize data and prepare the final report.

Table 11 gives the emission results for HC, CO, NO_x, PM, and brake specific fuel consumption (BSFC) obtained for each of the tests. The average for each set of triplicate hot start transient tests was also included for each fuel.

TABLE 11
		BSFC,
TEST	TRANSIENT EMISSIONS, g/hp-hr	lb/hp-	WORK,
NUMBER	CO2	THC	CO	NOX	PM	hr	hp-hr
R1	538.0	2.437	0.077	4.621	0.183	0.378	24.39
R2	538.1	2.432	0.081	4.620	0.182	0.378	24.39
R3	539.1	2.530	0.083	4.620	0.182	0.378	24.39
Average	538.4	2.466	0.080	4.621	0.183	0.378	24.39
C4	539.6	2.122	0.075	4.540	0.147	0.388	24.35
C5	540.4	2.026	0.071	4.538	0.146	0.389	24.35
C6	540.3	2.026	0.071	4.542	0.148	0.389	24.36
Average	540.1	2.058	0.072	4.540	0.147	0.388	24.35
C7	539.0	2.121	0.070	4.513	0.148	0.388	24.39
C8	539.9	2.061	0.066	4.512	0.149	0.388	24.38
C9	539.5	1.997	0.070	4.523	0.149	0.388	24.38
Average	539.5	2.060	0.069	4.516	0.149	0.388	24.38
R10	539.7	2.485	0.085	4.597	0.188	0.379	24.39
R11	539.9	2.551	0.086	4.600	0.188	0.379	24.38
R12	539.6	2.469	0.087	4.615	0.190	0.379	24.40
Average	539.7	2.502	0.086	4.604	0.189	0.379	24.39
R13	537.1	2.543	0.078	4.567	0.183	0.377	24.41
R14	538.0	2.462	0.079	4.568	0.185	0.378	24.43
R15	538.1	2.438	0.081	4.584	0.184	0.378	24.42
Average	537.7	2.481	0.079	4.573	0.184	0.377	24.42
C16	539.2	2.035	0.068	4.513	0.146	0.388	24.36
C17	538.9	2.059	0.071	4.514	0.149	0.388	24.35
C18	539.9	2.143	0.073	4.526	0.148	0.388	24.35
Average	539.3	2.079	0.071	4.518	0.148	0.388	24.35
C19	532.1	2.045	0.064	4.432	0.129	0.383	24.40
C20	532.9	2.026	0.067	4.436	0.144	0.383	24.40
C21	532.9	2.029	0.069	4.447	0.148	0.383	24.38
Average	532.7	2.033	0.067	4.438	0.141	0.383	24.39
R22	534.6	2.558	0.082	4.553	0.182	0.375	24.38
R23	535.3	2.558	0.085	4.561	0.190	0.376	24.38
R24	535.7	2.496	0.087	4.564	0.186	0.376	24.39
Average	535.2	2.537	0.085	4.559	0.186	0.376	24.38
R25	528.2	2.485	0.077	4.482	0.187	0.371	24.48
R26	529.0	2.564	0.080	4.493	0.187	0.371	24.48
R27	529.3	2.475	0.082	4.502	0.190	0.372	24.48
Average	528.8	2.508	0.080	4.492	0.188	0.371	24.48
C28	532.9	2.155	0.066	4.437	0.151	0.383	24.37
C29	532.9	2.088	0.066	4.440	0.152	0.383	24.37
C30	534.0	2.207	0.068	4.447	0.151	0.384	24.37
Average	533.3	2.150	0.067	4.441	0.151	0.384	24.37

Table 12 shows the statistical approach for comparing the emission results. With this approach, the average for each of the triplicate results from the 21 individual tests with the candidate fuel, Fuel C (Xc), were compared to the average for each of the triplicate results for 21 individual tests with the average reference fuel, Fuel R (XR), by using the calculations describe above with X_C<X_R+δ−(S_p×√2/η×t(a, 2n−2)).

TABLE 12
Statistical Criteria	HC	CO	NOx	PM
Number of Test	14	14	14	14
Points, na
C Average, Xcb	0.082	2.509	4.540	0.187
R Average, XRb	0.068	2.080	4.463	0.147
Tolerance Level, δc	0.002	0.050	0.045	0.004
Pooled std. Dev., Spb	0.003	0.033	0.065	0.003
Sqrt of 2/n	26	26	26	26
Student's t, td	1.058	1.058	1.058	1.058
Adjusted R Average,	0.082	2.546	4.560	0.189
Adj. XRb,e
Is Xc < Adj. XR	Yes	Yes	Yes	Yes
Percent Reduction, r	17.5	18.3	2.1	22.1
aFor alternative 1, n = number of tests (plus reference candidate)
bUnits are in g/bhp-hr
cTolerance level is 1 percent for NOx and 2 percent for HC, CO, and PM
ddf = 2(n − 1)
One-sided student's t for 2n − 2 degrees of freedom and significance level of 0.15
Adj. XR = XR + δ − (Sp × √2/η × t(a, 2n − 2)) where t(a, 2n − 2) is 1.055

As shown, the candidate fuel was found to decrease the NO_x emissions by 2.1 percent when compared to the reference fuel. The PM emissions were decreased by about 22 percent and average HC and CO were lower (17.5 and 18.3 percent lower, respectively).

The contents of all references (including literature references, issued patents, published patent applications, and co-pending patent applications) cited throughout this application are hereby expressly incorporated herein in their entireties by reference. Unless otherwise defined, all technical and scientific terms used herein are accorded the meaning commonly known to one with ordinary skill in the art.

Claims

1. A biodiesel fuel mixture composition comprising: 18-21 wt. % of biodiesel, the biodiesel having: a cetane number of 47 or greater;a sulfur content of 15 ppm or less;a flash point of 190° F. or greater; anda fatty acid methyl ether (FAME) content of 95 volume % or greater; and79-82 wt. % of a base petroleum diesel fuel, the base petroleum diesel fuel having: between 10 wt % and 25 wt % aromatics;7 wt % polycyclic aromatics or less;a cetane number between 45 and 60;a sulfur content of 15 ppm or less;a flash point of 125° F. or greater; anda FAME content of 5 volume % or less; andfrom 1000 to 3500 ppm 2-ethylhexyl nitrate.

2. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture decreases NOx emissions of an engine by 1 to 7%.

3. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture decreases total particulate matter emissions of an engine by 20 to 25%.

4. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture decreases CO emissions of an engine by 15 to 25%.

5. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture decreases total hydrocarbon emissions of an engine by 15 to 25%.

6. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture has a cetane number of 45 to 70.

7. The biodiesel fuel mixture of claim 6, wherein the biodiesel fuel mixture has a cetane number of 45 to 65.

8. The biofuel mixture of claim 1, wherein the biodiesel fuel mixture comprises 2-20% aromatics by volume.

9. The biodiesel fuel mixture of claim 1, wherein the biodiesel fuel mixture comprises less than 7% polycyclic aromatics by weight.

10. The biodiesel fuel mixture of claim 9, wherein the biodiesel fuel mixture comprises 0.2-5% polycyclic aromatics by weight.

11. The biofuel mixture of claim 1, wherein the biodiesel fuel includes 12-15 wt. % of a first biodiesel fuel and 6-8 wt. % of a second biodiesel fuel.

12. The biodiesel fuel mixture of claim 11, comprising: 13 wt. % of the first biodiesel fuel;7 wt. % of the second biodiesel fuel; and80 wt. % of the base petroleum diesel fuel.

13. The biodiesel fuel mixture of claim 1, wherein a fatty acid methyl ester content of the biodiesel fuel mixture is 19 to 21 wt. %.

14. The biodiesel fuel mixture of claim 1, wherein a viscosity of the biodiesel fuel mixture at 40° C. is 1.9 to 4.1 centistokes.

15. The biodiesel fuel mixture of claim 1, wherein the 2-ethylhexyl nitrate is present in an amount of 1000, 1500, 2000, 2500, 3000, or 3300 ppm.

16. The biodiesel fuel mixture of claim 15, wherein the 2-ethylhexyl nitrate is present in an amount of 3300 ppm or 3000 ppm.

17. A biodiesel fuel mixture composition comprising: 15-25 wt. % of biodiesel, the biodiesel having: a cetane number of 47 or greater;a sulfur content of 15 ppm or less;a flash point of 190° F. or greater; anda fatty acid methyl ether (FAME) content of 95 volume % or greater; and75-85 wt. % of a base petroleum diesel fuel, the base petroleum diesel fuel having: between 10 wt % and 25 wt % aromatics;7 wt % polycyclic aromatics or less;a cetane number between 45 and 60;a sulfur content of 15 ppm or less;a flash point of 125° F. or greater; anda FAME content of 5 volume % or less; andfrom 1000 to 3500 ppm 2-ethylhexyl nitrate.

18. The biodiesel fuel mixture of claim 17, further comprising about 300 ppm di-tert-butyl peroxide and about 300 ppm phenylenediamine.

19. The biodiesel fuel mixture of claim 17, wherein an increase in 2-ethylhexyl nitrate concentration results in a decrease in the NOx emissions of an engine.