07PFL-655

Computational Analysis of Biodiesel Combustion in a LowTemperature Combustion Engine using Well-Defined Fuel Properties
Jonathon P. McCrady, Valerie L. Stringer, Alan C. Hansen, and Chia-fon F. Lee
University of Illinois at Urbana-Champaign
Copyright 2007 SAE International

ABSTRACT
Biodiesel fuel can be produced from a wide range of source materials that affect the properties of the fuel. The diesel engine has become a highly tuned power source that is sensitive to these properties. The objectives of this research were to measure and predict the key properties of biodiesel produced from a broad range of source materials to be used as inputs for combustion modeling; and second to compare the results of the model with and without the biodiesel fuel definition. Substantial differences in viscosity, surface tension, density and thermal conductivity were obtained relative to reference diesel fuels and among the different source materials. The combustion model revealed differences in the temperature and emissions of biodiesel when compared to reference diesel fuel.

from one feedstock to another can vary significantly. This variation occurs due to the presence of different fatty acids in the stock oil or fat. Several methods have been developed to calculate the properties of a biodiesel fuel based upon its fatty acid composition [1-7]. The properties predicted include the critical properties, density, viscosity, vapor pressure, surface tension, heat of vaporization, and enthalpy. Aside from the critical properties, all of these physical parameters are influenced by temperature. Yuan [8] was able to compile the methods for computing these properties into a single program known as BDProp. The only input required was the fatty acid composition of the fuel. These property estimations were based on experiments of different kinds of liquids and relied on various equations fitted to the data. Yuan [8] incorporated a limited number of source materials in his study, thus resulting in the equations not being able to represent a broader range of fatty acid compositions. The properties selected for measurement were density, surface tension, and viscosity. These properties were chosen since they have a large influence on the atomization and combustion of the fuel. Another property, thermal conductivity, was selected for estimation only as present measuring techniques for this property tend to be unreliable. Thermal conductivity is another property needed by combustion modeling software. This property gives an indication of how well heat flows through a substance. As the heat flows through the fuel, the temperature will change as well. All of these processes are temperature dependent, making thermal conductivity a very important property. The program BDProp outputs the values of the physical properties versus temperature in a file format suitable for the KIVA-3V combustion modeling code. BDProps output is the fuel definition needed by KIVA to analyze the combustion. The primary objectives of this research were the following: first to measure and be able to predict the key properties of biodiesel produced from source materials

INTRODUCTION
Biodiesel is a fuel comprising the mono-alkyl esters of long-chain fatty acids derived from vegetable oils and animal fats. This renewable fuel is touted as a replacement for petroleum diesel fuel. It has been shown to significantly reduce particulate matter, hydrocarbon, and carbon monoxide emissions. These advantages have led to greater research in recent years. Tax credits and incentives have been given to those that produce and market biodiesel fuels. However, several issues remain that have slowed widespread use of biodiesel. These issues include quality assurance in production, cold flow properties and oxidative stability. However, looking beyond these issues, it is also evident that very little work has centered on adapting engines to run specifically on biodiesel. Opportunities exist to adjust combustion control strategies in order to take advantage of the unique properties of biodiesel that are attractive for compression-ignition. In order to pursue these strategies it is important to measure and quantify the properties of biodiesel and to explore in-depth its combustion characteristics. Biodiesel can be produced from many different types of oils and fats. The physical properties of a biodiesel fuel

with a broad range of fatty acid compositions that are inputs for a Low Temperature Combustion (LTC) model developed using the KIVA-3V code; and second to compare the combustion of two different biodiesel fuels with a petroleum-based diesel fuel with the aid of this model.

SELECTION OF BIODIESEL SOURCE MATERIALS

Five source materials for biodiesel were selected on the basis of their substantial differences in fatty acid composition. Soybean and rapeseed oils were included in this selection as they are the most commonly used oils for biodiesel production in the U.S. and in Europe respectively. Table 1 provides a summary of the typical fatty acid profiles of these oils [8]. In the fatty acid specification, C8 for example refers to the fatty acid having a molecule comprising a chain of eight carbon atoms, while the 0 indicates that there are no double bonds in the molecule. Soybean oil contains a major component of C18 acids with a predominance of C18:2 linoleic acid. Rapeseed oil is dominated by C22:1 erucic acid with the remainder of the acids being primarily C18. In comparison coconut oil consists mainly of C12:0 lauric acid, a shorter chain saturated acid, with the remaining acids being mostly saturated as well. The main fatty acid in palm oil is C16:0 palmitic acid, a longer chain acid than what predominates in coconut oil. However, it also has a substantial amount of C18:1 oleic acid. The composition for beef lard shows that C18:1 oleic acid represents about half the total percentage, followed by C16:0 palmitic acid. C18:0 stearic acid comprises almost 20% of the beef lard. Table 1 Fatty acid profiles of five biodiesel feedstocks [8] Fatty Acid C8:0 C10: 0 C12: 0 C14: 0 C16: 0 C18: 0 C18: 1 C18: 2 C18: 3 C22: 1 Soybea n 0.0 0.0 0.0 0.001 0.103 0.047 0.225 0.541 0.083 0.0 Rapesee d 0.0 0.0 0.0 0.0 0.027 0.028 0.219 0.131 0.086 0.509 Coconu t 0.083 0.06 0.467 0.183 0.092 0.029 0.069 0.017 0.0 0.0 Palm 0.001 0.001 0.009 0.013 0.439 0.049 0.39 0.095 0.003 0.0 Beef Lard 0.0 0.001 0.001 0.033 0.252 0.192 0.489 0.027 0.005 0.0

The large variation in fatty acid composition amongst these source materials will help to provide a more reliable prediction of fuel properties that are dependent on fatty acid composition. These fatty acid profiles are assumed to be very similar to what the actual fuel samples contain, but since variability can exist within each feedstock, there may be small differences the actual and typical fatty acid compositions. The source material can have a big impact on the ignition quality of biodiesel [9-12]. Studies have shown that the cetane number of biodiesel decreases with increasing unsaturation and increases with increasing chain length [11]. Cetane numbers for C12-C18 saturated fatty acids are typically above 60 [10], while there is a rapid decrease in cetane number with increasing double bonds. For example the cetane number for C18 decreases from well above 60 for C18:0 to below 25 for C18:3 [10]. In line with these trends, studies show that soybean and rapeseed methyl esters have cetane numbers in the range of 50-55, while the methyl esters of the remaining three source materials are typically above 60 [10]. These variations highlight the effect of the source material on the combustion process in a diesel engine.

PREDICTING THERMAL CONDUCTIVITY

The thermal conductivity of the five samples of biodiesel was estimated by first establishing the thermal conductivity of each individual methyl ester. Poling et al. [4] used the method developed by Sastri:

L = b a m
1 Tr m = 1 1 T br
n

Where L is the thermal conductivity in W/m-K, b is determined by the group contributions as specified by Sastri, Tr is the reduced temperature, and Tbr is the reduced temperature at the boiling point. Almost 200 liquids were tested using this method with the average error being 8.6% [4]. The boiling point of individual methyl esters has been ascertained [6]. Several methyl esters have had their boiling points determined [10]. Yuan et al. [6] were able to correlate the boiling point of other methyl esters to the number of carbon atoms with a fairly strong correlation. A 3C correction was applied to the methyl esters with one degree of unsaturation. The boiling point for methyl esters of higher degrees of unsaturation has been found to be independent of the degree of unsaturation [10]. The critical temperature of each methyl ester was determined using the Joback modification of Lydersens method [1]:

Tc = Tb 0.584 + 0.965 T ( t )

Where Tc is the critical temperature in Kelvin, Tb is the boiling point in Kelvin, and T is obtained by summing the group contributions as determined by Joback [1]. The Li method for computing the thermal conductivity of the liquid mixture was adapted from Reid et al. [1]:

m = i j ij
i =1 j =1

ij = 2 i 1 + j 1 i =
xiVi

touched the hydrometer. The density was then found by multiplying by the reference density of water at 15.6C. The five fuels were placed into graduated cylinders and a water bath was used to control the temperature. The same water bath for the viscosity measurements was used to control the temperature of the fuel samples in each cylinder for the density measurement. The water bath allowed for measurements at 20, 40, 60, 80, and 87C. Three measurements were made at each temperature to ensure consistency in the data and the average of these measurements was used as the accepted value. SURFACE TENSION - The surface tension was measured using a fast bubble technique [13] with two syringes. The Laplace equation from Atkins and de Plata [14] was used to compute the surface tension.

x V
j j =1

Where xi is the mole fraction and Vi is the molar volume of the pure component. It was noted that if the liquid mixture is nonaqueous, the molar volume can be replaced with the critical volume without affecting the results significantly. Biodiesel is a nonaqueous solution, so the critical volume was used in place of the molar volume. The critical volume was calculated again using the Joback modification of Lydersens method [1]:

Pbubble = Phyd +

4 D

Vc = 17.5 + V
V is calculated by summing the group contributions as determined by Joback giving the critical volume in mL/mol [1].

Pbubble is the pressure inside the bubble (Pa), Phyd is the hydrostatic pressure acting on the bubble (Pa), D is the diameter of the bubble (m) and is the surface tension (N/m). With two syringes set at the same depth, the hydrostatic pressure acting on the bubbles is exactly the same and the surface tension will be the same as well since the temperature of the solution is uniform. With known diameters on each bubble, the surface tensions can be equated to find the hydrostatic pressure acting on each bubble:

Phyd =

Pbubble ,l arg e Dl arg e Pbubble ,small Dsmall Dl arg e Dsmall

PROPERTY MEASUREMENT
MATERIALS AND METHODS - Five biodiesel samples were prepared from feedstocks of soybean oil, rapeseed oil, coconut oil, palm oil, and beef lard. Methanol was used as the alcohol in the transesterification process, forming methyl esters. VISCOSITY - The viscosity of the biodiesel fuels was measured using a Cannon-Fenske type 75 viscometer. The efflux time of the fuel through the tube was measured with a stopwatch accurate to 0.01s. A Bluebird-M constant temperature water bath was used to control the temperature of the viscometer to within +/0.1C. The viscosity was measured at five temperatures, 20, 40, 60, 80, and 100C for each fuel. At each temperature, three measurements were made to ensure that the measured viscosity was a consistent value. The average of these values was used as the actual viscosity at each specific temperature. DENSITY - A hydrometer referenced to 15.6C was used to measure the liquid density. It was scaled between specific gravities of 0.650 and 1.000 in increments of 0.050. The specific gravity was found by reading the meniscus of the fuel at the point where it The subscripts small and large indicate the syringe size. To determine the surface tension, the maximum bubble pressure was found for each syringe and applied to the above equations. The maximum air pressure was found by controlling the airflow through each syringe until one bubble every 3-4 seconds was being emitted by a syringe. This was done by restricting the airflow with needle valves in one syringe and opening the needle valves on the other syringe. The maximum pressure for each of a series of 5 to 6 bubbles was recorded and averaged to the representative maximum bubble pressure. The temperature of the system was controlled by a Julabo FP40 water bath with a temperature control of +/-0.1C. The temperature range of the bath allowed measurements to be taken at 20, 40, 60, 80, and 90C.

COMBUSTION MODEL
MODEL DETAILS The combustion model used in this investigation was KIVA 3V-R2 code [15]. The KIVA code is a threedimensional CFD program used to simulate engine operation. Modifications to the KIVA code include the

modified Shell ignition model, developed by Halsted et al. [16] blow-by model, developed by Zhao [17] and extended Zeldovich mechanism [18]. One other major improvement made to the KIVA-3V-R2 code was the addition of the KH-RT breakup model [8,19] which was used to simulate the breakup of biodiesel fuel droplets. SHELL IGNITION MODEL For the Low Temperature Combustion (LTC) engine used in these combustion simulations, the fuel ignition is mainly controlled by chemical kinetics. The Shell ignition model is a multi-step kinetics model that is able to predict low-temperature chemistry, according to eight reactions:
q RH + O2 2 R *

0.34 + 0.38We1.5 (1 + Z ) 1.4T 0.6

l r 3

where We is the gas Weber number, Z is the Ohnesorge number for the liquid, and T is the Taylor number. The characteristic K-H wave breakup time is defined as

b =

3.788 B1 r

where B1 is a constant, given a value of 1.0. In a similar way, the Rayleigh-Taylor instability also focuses on wave development. A droplet that has a high initial velocity, at the exit of the injector tip, will experience drag forces and will rapidly decelerate. The R-T wavelength, frequency and wave number can be written as

p R * R + P + heat

1 R * p R * + B

fK

4 R * p R * +Q

f K

RT =

B2
K RT
2[ g t ( l g )]1.5 3 3 ( l + g )

2 R * +Q p R * + B

f K

p B 2R *

3 R * p end

f K
K

RT =

f 2 R * end

where RH is the fuel in the form CnH2mOk, R* represents the radicals, P represents the products such as CO, CO2 and H2O, B represents the branching agent and Q represents the intermediate species. The rate constants K follow Arrhenius kinetics and were determined empirically. The f rate terms are also expressed in terms of local fuel and oxidizer concentrations. Though the Shell model was originally developed to predict knock in SI engines, it has proved valuable in predicting ignition of diesel fuel as well. KH-RT BREAKUP MODEL The KH-RT breakup model combines two processes into one model. Using the approach of Reitz and Diwakar [24], the liquid injection is simulated using a blob injection method, and the subsequent breakup is simulated using a wave model. The new droplet radius can be defined as:

K RT =

g t (l g ) 3

where gt is the acceleration in the direction of droplet travel. The R-T characteristic breakup time is defined as

RT =

B3 RT

where B3 = 1.0. The K-H and R-T models will compete for the breakup of the droplet. If the wavelength is less than droplet radius, the wave was assumed to grow on the surface of the droplet and R-T breakup would occur when the time reached the R-T breakup time. When the droplet radius is bigger than the K-H wavelength, the droplet would break up according to the K-H model. MODEL APPLICATION

rc = B0
where B0 is a constant equal to 0.61 and represents the wavelength that corresponds to the fastest growing Kelvin-Helmholtz wave frequency, , which can be written as

The BDProp program [8] was used to estimate the fuel properties of biodiesel made from soybean oil and rapeseed oil. These two sets of fuel properties were then entered into the KIVA code as an addition to the fuel library. Simulations were completed for soybean oil

biodiesel and rapeseed oil biodiesel as these two source materials are the most widely used in the U.S. and Europe at present. The chosen physical properties of the fuel were then measured. Measurements indicated that the BDProp calculations, especially at lower temperatures, varied from actual measured values. The measured fuel properties were therefore put into KIVA to provide more accurate combustion modeling. The fuel data used in KIVA for these second simulations were a combination of measured properties, from 290-390 K and calculated properties taken from BDProp at temperatures higher than 390 K. These simulations were completed to confirm that BDProp can be considered sufficiently accurate for combustion simulations. Table 3: Engine Specifications Bore Stroke Displacement volume Connecting rod length Number of nozzles Compression Ratio Engine Speed Start of Injection Injection Duration Fuel Quantity Swirl Ratio 7.0 cm 7.8 cm 300 cc 13.26 cm 6 19.5:1 1500 RPM 335 CA 10 CA 0.00877 g 2.5

Further details on the engine design and simulations using this engine have previously been published [2023]. The engine mesh supplied for these simulations contains 6607 cells and can be seen in Figure 1.

RESULTS AND DISCUSSION

PROPERTY MEASUREMENTS AND PREDICTIONS The measurements of viscosity, density and surface tension for all five biodiesel samples showed large differences relative to the reference diesel fuel. Also the predicted thermal conductivities for the biodiesel samples were substantially different than the reference fuel. Viscosity - The measured viscosities are shown in Figure 2 for each of the biodiesel fuels varying with temperature. Typical viscosity values for #2 diesel fuel are included [7]. As expected the measured values decrease with temperature in all cases. All five methyl esters have higher viscosities than the no. 2 reference diesel fuel and even within the methyl esters there is a large variation. The coconut oil ester had a noticeably lower viscosity, followed by soybean oil. Only the coconut oil was able to meet the maximum limit of the ASTM standard.
9
Soybean Rapeseed Coconut Palm Beef Lard #2 Diesel

8 Kinematic Viscosity,mm^2/s 7 6 5 4 3 2 1 0
20 30 40 50 60 70 80 90 100 Max. limit ASTM D975 @ 40C

Temperature, C

Figure 2 Variation with temperature of measured kinematic viscosity of biodiesel made from five source materials compared to a reference diesel fuel Surface tension - Surface tension measurements also revealed substantial differences between the methyl esters and no. 2 reference diesel fuel as illustrated in Figure 3. Again the methyl esters had higher surface tensions with coconut oil also having the lowest values, followed this time by palm oil. Density - The measured values of density are shown in Figure 4. Again, the densities decrease with temperature as expected. The densities of the biodiesel fuels are all substantially higher than for #2 diesel fuel, which is also expected from published measurements [3]. There is some variability among the different biodiesel fuels with the soybean and rapeseed oil methyl

Figure 1 Three-dimensional mesh for Ford DIATA engine For each test case, the fuel was injected at 335 CA, for a duration of 10. The engine mesh used in these simulations is for a Ford DIATA engine with total displacement volume of 300 cc. Table 3 shows the dimensions and operation conditions of the engine in the simulation. In order to reduce computation time, only one sixth of the cylinder was modeled. This 60 sector was chosen for its symmetric characteristics such that one injection nozzle was included in each sector.

esters exhibiting the higher values. Coconut oil in this case is in the middle of the group.
Thermal Conductivity, W/m-K

0.25 Soybean Coconut Beef Lard C14H30 Rapeseed Palm #2 Diesel

0.20

34 32 Surface Tension, mN/m 30 28 26 24 22 20

20

Soybean

Rapeseed

Coconut

Palm

Beef Lard

#2 Diesel

0.15

0.10

0.05

0.00 0 100 200 300 400 500 600 700 Temperature, K

30

40

50

60

70

80

90

100

Temperature, C

Figure 5: Variation with temperature of predicted thermal conductivity of biodiesel made from five source materials compared to no. 2 reference diesel fuel and tetradecane C14H30 reference diesel fuel COMBUSTION MODELING RESULTS The property modifications made to both the soybean biodiesel and rapeseed biodiesel show practically no discernible difference in peak pressure or temperature. Figure 5 shows the identical shape of the soybean biodiesel pressure curve.

Figure 3 Variation with temperature of measured surface tension of biodiesel made from five source materials compared to no. 2 reference diesel fuel
0.90 0.88 0.86 0.84 0.82 0.80 0.78
15 25 35 45 55 65 75 85 95

Soybean Palm

Rapeseed Beef Lard

Coconut #2 Diesel

Density, g/cm^3

Temperature, C

Figure 4 Variation with temperature of measured density of biodiesel made from five source materials compared to #2 diesel reference fuel Thermal conductivity - The predicted thermal conductivity values of the biodiesel fuels are illustrated in Figure 5 across a broad range of temperatures up to the critical temperature. Predictions for both #2 diesel fuel and a C14H30 reference diesel fuel are included over a shorter temperature range than for the methyl esters. Both diesel fuels have lower thermal conductivities than the methyl esters. Coconut oil stands out again with the lowest conductivity of the five methyl esters. Rapeseed and soybean oils tend to have the higher conductivities. As expected [1], the thermal conductivity decreases with temperature in all cases. The decrease in value is approximately linear up to approximately 500 K for all cases. Thereafter for coconut oil methyl ester and to a much lesser extent the other fuels the rate of decrease increases. As stated previously [1], the error in the estimation of the pure liquids is 8.6% and the liquid mixture prediction is regarded as acceptable.

Figure 6: Comparison of original and modified soybean biodiesel fuels. From the above figure, we can conclude that the BDProp predictions of viscosity, vapor pressure, and surface tension are accurate within the range of 290-390 K for combustion modeling. Though the estimated properties vary slightly from the measured values, these differences seem to have no effect on the combustion simulation for the fuel. Comparisons between the three fuel types, however, show distinct differences between diesel fuel and biodiesel fuels. The diesel fuel seems to ignite earlier than either of the two biodiesel fuels. Because of the earlier ignition, the resulting temperature and pressure in

the diesel simulation are lower than for the biodiesel cases. This could be of major concern, especially for emissions, because the pollutant species tend to be formed at higher temperatures. The pressure for either of the biodiesel fuels increases drastically because ignition occurs much closer to top-dead-center for the engine. In this situation, the gases within the engine cylinder have been compressed to a high temperature. At the point of ignition, the fuel vapor, which had a high temperature, will increase to a much larger value because of the conditions prior to combustion. This can be seen by completing a simple energy balance. All three curves do show a trend toward premixed combustion, which is evidenced by the very sharp, and nearly vertical, curve just at the beginning of ignition.

ignition occurs. The peak temperatures, seen in the red colors, are located in very distinct areas of the cylinder. The diesel fuel also generates a higher local temperature while maintaining a lower volume-averaged temperature and pressure (as shown in Figure 7). The higher local temperatures with the diesel fuel may explain the higher levels of NOx produced, as shown in Figure 10.

Figure 7 Comparison of pressure traces for diesel, soybean biodiesel and rapeseed biodiesel fuels In the results shown in Figure 7, the soybean biodiesel produces the highest pressure, with rapeseed biodiesel just slightly lower. The pressure curves for both biodiesel fuels show a higher pressure than either amount of combusted diesel fuel. The pressure results shown are averaged over the volume of the cylinder. Computational images can also be used to investigate the combustion characteristics. In Figure 8 the temperature distributions of soybean biodiesel and No. 2 diesel fuel are compared at the same crank angles. The images on the left are from a simulation using soybean biodiesel, and the images on the right are from the same simulation with No. 2 diesel fuel. In both cases, the fuel injected travels towards the bowl region, and ignites there before the flame propagates through the rest of the cylinder. In this case with injection at 335 CAD, the diesel fuel seems to impinge on the wall of the cylinder and stay closer to the wall and bowl region than the biodiesel fuel. This can especially be seen in the image from CA = 360 CAD when ignition has occurred. The biodiesel case, seen on the left, shows good mixing of the fuel across the cylinder volume. Because the fuel is well-mixed prior to combustion in keeping with the LTC strategies, the pressure and temperature peak very rapidly when Figure 8 Temperature distribution for soybean biodiesel (left) and No. 2 diesel (right) The emissions of these three fuels also show wide ranges of difference. Biodiesel is expected to produce less soot than traditional diesel fuel by as much as 40%, which makes it a promising alternative to diesel. The combustion simulations completed in KIVA show this expectation is true. Figure 9 is a plot of the soot formed during combustion of soybean and rapeseed biodiesel as well as for two different masses of No. 2 Diesel fuel. A total of 0.00877 g of biodiesel need to be injected to maintain 2 bar IMEP for this engine, but only 0.00514 g of No. 2 Diesel fuel are necessary at this same load. The difference in masses is attributed to the lower energy content in biodiesel; therefore more biodiesel fuel is required to maintain the same load.

Simulations of diesel fuel were completed with both masses to provide more details for comparison. As can be seen, the soot formed by diesel combustion with the higher mass is almost 10 times as high as that for either of the biodiesel fuels. This trend can be seen in Figure 9. For the lesser mass of diesel injected, the amount of soot produced reduces, but still is about 3 times as high as the soot generated with the biodiesel fuels. One explanation for the high level of soot formation with the greater mass of diesel fuel is that this will create an overall fuel-rich condition in the cylinder. Operating an engine fuel rich often tends to increase the amount of soot formed in that engine.

The reduced mass of diesel at 0.00514 g has the same energy content as 0.00877 g of biodiesel. The use of BDProp has proven to be effective in capturing the differences between biodiesel fuels as well as the differences between organic fuels such as soybean or rapeseed biodiesel and petroleum fuels such as diesel.

CONCLUSIONS
The measurements of key biodiesel fuel properties for combustion modeling showed large differences relative to petroleum-based diesel fuel as well as among different source materials. The same result applied to the predicted thermal conductivity. However, the differences between the measurements and BDProp calculations for properties of the biodiesel, known only in the range of 290-390 K, do not seem to affect the outcome of the combustion simulations. Current LTC simulations predict that biodiesel will generate a higher in-cylinder temperature and pressure and that soot emissions from a diesel engine will be reduced with the use of biodiesel. Image processing also predicts that the diesel and biodiesel fuels will behave differently after injection during the vaporization process. Future work will focus on model verification with the aid of optical and metal engine tests.

Figure 9: Soot formation for diesel, soybean biodiesel and rapeseed biodiesel.

ACKNOWLEDGMENTS
This work was supported in part by the Department of Energy Grant No. DE-FC26-05NT42634, by Department of Energy GATE Centers of Excellence Grant No. DEFG26-05NT42622, and by the Ford Motor Company under University Research Program.

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