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pubs.acs.org/EF

Comparison of Ethanol and Butanol as Additives in Soybean Biodiesel

Using a Constant Volume Combustion Chamber
Haifeng Liu,, Chia-fon Lee,*, Ming Huo, and Mingfa Yao

State Key Laboratory of Engines, Tianjin University, Tianjin 300072, Peoples Republic of China
Department of Mechanical Science and Engineering, University of Illinois at Urbana
Champaign, Urbana, Illinois 61801, United States
ABSTRACT: To investigate the eects of dierent alcohol additives in biodiesel fuel on the spray, combustion characteristics, and
soot formation and oxidation, a detailed comparative study between the butanol
biodiesel blend and the ethanol
biodiesel blend
was carried out in an optical constant volume combustion chamber. Two dierent volumetric blend fuels were tested in this study
with dierent ambient temperatures at the start of injection (from 800 to 1200 K). The volumetric ratios were the 20% butanol/80%
soybean biodiesel referred to as B20S80 and 20% ethanol/80% soybean biodiesel referred to as E20S80. Results demonstrated that
the microexplosion occurred for B20S80 and E20S80 fuels at 800 and 900 K ambient temperature because of the volatility dierence
between the additives (butanol or ethanol) and the base fuel (biodiesel). The E20S80 fuel presented higher peak pressure and
shorter combustion duration compared to the B20S80 fuel. The autoignition was earlier for the B20S80 fuel at 1000 and 1200 K
ambient temperature, while the autoignition of the B20S80 and E20S80 fuels was nearly the same at 800 K ambient temperature.
The E20S80 fuel had a lower ame luminosity compared to the B20S80 fuel. The soot distribution was increased downstream of the
spray jet with a higher ambient temperature for both tested fuels, and E20S80 had a lower value of normalized time-integrated soot
mass (NTISM). Therefore, E20S80 has more advantages to reduce the soot emission compared to the B20S80 fuel. Also, increasing
the ambient temperature from 800 to 1200 K led to a rapid increase in the value of NTISM for both tested fuels. Therefore, a lower
ambient temperature with the piston at top dead center (TDC) should have more advantages to combustion and soot control in a
real diesel engine.

1. INTRODUCTION
Diesel fuel is a specic fractional distillate of petroleum fuel oil
and is largely consumed by the transportation sector. Alternatives
that are not derived from petroleum, such as biodiesel, are
increasingly being developed and adopted. Biodiesel is dened
as the monoalkyl esters of long-chain fatty acids derived from
various feedstocks, such as vegetable oil, animal fat, algae, etc.
Biodiesel has many similar properties to diesel fuel, and it can
blend with conventional diesel fuel in any proportion. Studies
with various biodiesel blend ratios or the neat biodiesel have
demonstrated that biodiesel-fueled diesel engines could reduce
emissions of carbon monoxide (CO), total hydrocarbons
(THCs), and particulate matter but slightly increase brakespecic fuel consumption because of the reduction in heating
value, while the power output for biodiesel was almost the same
as that for diesel fuel.1
9 Most of the studies reported a slight
increase in nitrogen oxides (NOx) emissions using biodiesel
fuels. However, this NOx emissions problem could be eliminated
by advanced injection strategies and exhaust gas recirculation
(EGR).2,4,9 In addition, studies have also demonstrated that
biodiesel had low or no greenhouse gas emissions (in net) by the
well-to-wheels analysis.10,11 Thus, it can be seen that biodiesel is
able to be used as a substitute for diesel fuel in a diesel engine with
lower harmful gas emissions.
Most of the properties of biodiesel fuels are comparable to
those of diesel fuel, except for cloud point and pour point, which
indicate that the cold ow behavior of a fuel is poor. In addition,
the viscosity of biodiesel is higher than that of the diesel fuel, which
will aect the spray characteristics and subsequent combustion
r 2011 American Chemical Society

processes. Studies have demonstrated that the low-temperature

ow properties of biodiesel could be improved by blending
ethanol with various volumetric ratios (0
20%).12
14 Further,
a 20 vol % ethanol blending into biodiesel has been reported to
achieve improved combustion with a reduction in CO, THC,
NOx, and smoke emissions without aecting the break thermal
eciency.12,15 The addition of ethanol with a 10
30% blend
ratio decreased the droplet size and improved the atomization
performance of biodiesel fuel because of the lowered kinematic
viscosity.16
18
On the other hand, butanol is a very competitive alcohol to be
applied in diesel engines and is becoming popular recently.
Similar to ethanol, butanol is a biomass-based fuel that can be
produced by alcoholic fermentation of the biomass feedstocks. A
study has shown that the solubility of diesel
biodiesel
butanol
was higher than the solubility of diesel
biodiesel
ethanol at
temperatures of 10
30 C,19 and another study has also
demonstrated that ethanol
diesel depicted poor blending stability compared to butanol
diesel blends.20 The miscibility of
butanol with biodiesel was excellent compared to ethanol at a
wide range of operating conditions.21,22 Furthermore, fuel properties illustrated in Table 1 indicate that butanol has the potential
to overcome the drawbacks brought by ethanol in diesohol
fuels,19
26 i.e., higher heating value, less vapor lock tendency
because of lower volatility, less ignition problems because of
Received: January 20, 2011
Revised:
March 28, 2011
Published: March 28, 2011
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Table 1. Properties of Ethanol, Butanol, Soybean Biodiesel, and the Blend Fuels
properties

ethanola

butanola

soybean biodiesel

B20S80

E20S80

(ASTM method)

(ASTM method)

(ASTM method)

molecular formula

C2H5OH

C4H9OH

CH3OOCR

cetane number

25

51 (D 613)

49.2 (D 976)

47.8 (D 976)

octane number

108

96

oxygen content (wt %)

34.8

21.6

10

12.32

14.96

density at 15 C (g/mL)

0.795

0.813

0.887 (D 1298)

0.871 (D 1298)

0.869 (D 1298)

autoignition temperature (C)

434

385

363b

ash point at closed cup (C)

lower heating value (MJ/kg)

8
26.8

35
33.1

173.9 (D 93)
37.53 (D 240)

36.64

35.38

boiling pointc (C)

78.4

117.7

329.7 (D 1160)

318.6 (D 86)

303.5 (D 86)

stoichiometric ratio

9.02

11.21

12.5

12.24

11.80

latent heating at 25 C (kJ/kg)

904

582

200b

276.4

340.8

4.0 (D 445)

3.68 (D 445)

3.08 (D 445)

ammability limits (vol %)

4.3
19

1.4
11.2

saturation pressure at 38 C (kPa)

13.8

2.27

viscosity at 40 C (mm2/s)

1.08

2.63

total glycerin (wt %)

free glycerin (wt %)

0.142 (D 6584)
<0.001 (D 6584)

sulfated ash (wt %)

<0.01 (D874)

sulfur (ppm)

<1 (D 5453)

copper strip corrosion

1a (D 130)

carbon residue (wt %)

<0.020 (D 4530)

acid number (mg of KOH/g)

0.43 (D 664)

phosphorus content (ppm)

<1 (D 4951)

sodium and potassium combined (ppm)

water and sediment (wt %)

<5 (EN14112)
<0.05 (D 2709)

The properties of ethanol and butanol are from refs 24 and 25. b The value is from ref 26. c The boiling point for soybean biodiesel, E20S80, and B20S80
is the mid-boiling temperature.

lower latent heat, and higher cetane number. A study has

demonstrated that the viscosity of the biodiesel was decreased
by the butanol additives and the soot and NOx emissions
reduction with 20 vol % butanol blend in biodiesel.27 Further,
a detailed chemical kinetic reaction mechanism was proposed for
this biodiesel
butanol surrogate (methyl octanoate
butanol)
in a jet-stirred reactor, and the study has also indicated that the
methyl octanoate
butanol mixtures are less prone to emitting
acetaldehyde than the corresponding methyl octanoate
ethanol
mixtures oxidized in a jet-stirred reactor.28
On the basis of the literature survey, it can be found that the
benet of alcohol
biodiesel blends is its capability of osetting the
disadvantage of higher viscosity and worse cold ow behavior for
biodiesel and the lower cetane number for alcohols; thus, properties
of the blend fuels are similar to conventional diesel fuel. Meantime,
the spray and emission characteristics for neat biodiesel may be
improved by adding ethanol or butanol. However, there was few
reports on the detailed comparative study between the butanol
biodiesel blend and the ethanol
biodiesel blend in terms of
spray, combustion, and emissions. In this paper, two dierent blend
fuels, butanol/soybean biodiesel and ethanol
soybean biodiesel,
were tested in an optical constant volume combustion chamber. Mie
scattering, natural ame luminosity, and forward illumination light
extinction (FILE) were used to explore the spray, combustion
characteristics, and soot distribution, respectively, at various ambient
temperatures, ranging from 800 to 1200 K. The study is signicant
to reveal the eects of dierent alcohol additives in biodiesel fuel on
the spray, combustion characteristics, and soot formation and
oxidation.

2. EXPERIMENTAL SECTION
2.1. Experimental Setup. A constant volume chamber with
optical access was used in this study. The chamber has a bore of 110 mm
and a height of 65 mm. Figure 1a shows the schematic of the chamber
and soot measurement method. A fused silica (Dynasil 1100) end window
with a high UV transmittance down to 190 nm was installed opposite to
the injector. A Caterpillar hydraulic-actuated electronic-controlled unit
injector (HEUI) was mounted at the center of the chamber bottom, and
the configurations of the injector are listed in Table 2. The cylinder wall
was heated to 380 K by eight heaters before the test to mimic the wall
temperature of a diesel engine as well as to prevent water condensation
on the optical windows. The oil line and fuel line inside the chamber
head were kept at 350 K to simulate the situation in an actual engine. A
quartz pressure transducer (Kistler 6121) was embedded in the chamber
wall in conjunction with a dual mode differential charge amplifier for
recoding the in-chamber pressure during the experiments.
2.2. Laser Diagnostic Methods. The working principle of liquid
spray light scattering is the different reflective rates from the liquid
droplets and its surrounding background. The camera could observe
stronger reflection of the laser beam from spray, resulting in different
pixel values on the images; therefore, the spray behavior could be taken.
For the natural flame luminosity measurement, images were obtained by
a high-speed camera (Phantom V7.1) with a 105 mm focal length lens
(Nikkor), located above the chamber. A neutral-density filter was
adopted to fit the light intensity within the camera measurement range.
The forward illumination light extinction (FILE) method was used for
the soot distribution and two-dimensional (2D) time-resolved quantitative measurements, and it has been used to measure the total soot mass
in previous studies.23,29
33 Soot measurements using the light extinction
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Figure 1. Schematic of the constant volume chamber and light extinction by the soot cloud.

Table 2. Conguration of the HEUI Injector and the Condition of Fuel Injections
parameter

value

nozzle style

valve-covered orice

number of nozzle holes

spray angle (deg)

140

orice diameter (mm)

injection pressure (MPa)

0.145
134

injection duration (ms)

3.5

fuel volume (mm3)

120

fuel temperature (K)

350

method have been conducted in a number of studies,34
37 and the FILE

method shares a similar principle but requires only one window for
optical access, as explained in the following.
As seen in Figure 1b, without soot in the light path, only a part of the
light is reected back to the camera after the diuse reection. This
reected light is labeled as I0 and represents the light intensity reaching
the camera without the soot cloud. With the incident light labeled as Ii, it
is obtained by I0 = RIi, where R represents the ratio between the incident
light and the light collected by the camera after the diuse reection. It is
determined by surface roughness and optical properties. The reected
light should be much smaller than the incident light because of the
diuse reection character. With the soot cloud, the incident light will be
attenuated before it reaches the light diuser, as shown in Figure 1b. The
light intensity after the soot cloud is labeledR as I1, which obeys
Lambert
Beers law and is given by I = I1 exp(
L0 Kextdx), where Kext
is the extinction coecient for a cloud of soot (m
1) and L is the path
length of the light beam or the thickness of the soot cloud (m). After
reaching the light diuser, I1 will be further attenuated by the light diuse
reection. It will obey the same rule as without soot: I2 = RI1. The
reected light will then go through the soot cloud again and once more
be attenuated. The light recorded
R by the camera after the soot cloud is
now labeled as I; I = I2 exp(
L0 Kextdx). Combining the above relations
together, it obtains that the light intensity changes resulting from the
presence of soot are similar to Lambert
Beers law.
Z 2L
Kext dx
1
I I0 exp

0

.The only dierence is that the light extinction is related to 2L instead of

L because of the two passes through the soot cloud.

The extinction coecient for the soot cloud is related to the particle
number density, size, and optical properties. With the Rayleigh approximation, a simple expression can be obtained. The soot volume fraction
can be shown as
 
 

I0

I0
Cv
ln

2
ln
2LKa 1 Rsa
2LKe
I
I
,where Rsa is the scattering/absorption ratio. With the Rayleigh approximation, the extinction is mainly dominated by the absorption of soot
rather than the scattering; therefore, Rsa is equal to 0, is the wavelength
of monocolor light, Ka is the dimensionless absorption constant, which
can be calculated using the following formula with the Rayleigh
scattering approximation:
!
m2
1
36nk

3
Ka 6 Im 2
m 2
n2
k2 22 4n2 k2
Here, m is the refractive index of soot m = n ik and changes with the
composition of soot and the wavelength of light. The Rayleigh approximation is valid for soot measurements with primary soot sizes below
50 nm and laser wavelengths of 511 nm. The scattering/absorption ratio
can be assumed to be 0. The dimensionless extinction coecient Ke will
be the same as the dimensionless absorption coecient Ka. In this paper,
a value of 5.47 is adopted with m = 1.62 i0.66. The images recorded
with and without soot clouds are processed pixel by pixel to calculate the
soot volume fraction using eq 2. However, for a non-axisymmetric diesel
ame, the thickness of the soot cloud is unknown and what is obtained is
only a line-of-sight measurement as computed by CvL = (/2Ke)ln
(I0/I). If the area represented by each pixel is known as s and the soot
density is chosen as Fs = 2.0 g/cm3, the soot mass at each pixel will be
known as mi = FsCvLs. When all pixel values are summed together, the
total soot mass in the ame can be calculated. For the soot density, some
studies have demonstrated that the value was about 1.8
2.0 g/cm3.38
41 In
this paper, the soot density was chosen as 2.0 g/cm3 based on the recent
ultra-small-angle X-ray scattering work by Braun et al.40 and helium
pycnometry measurements by di Stasio.41
The current optical setup of FILE is shown in Figure 1a. The incident
light was supplied by a copper vapor laser (Oxford Lasers LS20-50). The
camera and laser were synchronized up to 15 037 frames/s to produce
time-resolved measurements at a resolution of 256  256 pixels. The
copper vapor laser has two-color output at 511 and 578 nm, with a power
ratio of 2:1. To lter out the light at 578 nm for this monochromatic light
extinction and suppress the ame emission, two interference lters at
510 and 515 nm with 10 nm full width at half-maximum (fwhm) were
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adopted. The two lters will achieve a 5 nm fwhm when aligned together.
The light emitted from the ber was condensed by an aspheric
condenser lens. The laser beam entered the constant volume chamber
via a reecting mirror of 6 mm in diameter placed in front of the
condenser lens.
2.3. Experimental Procedure. The test procedure was started by
filling the chamber to the premixed, combustible-gas mixture with a
specified density. The mixture, including acetylene (C2H2), oxygen, and
nitrogen, whose concentration can be precisely controlled through their
source pressure, was then ignited with a spark plug and burned to create
a high-temperature, high-pressure environment in the chamber. Acetylene was used as the combustible gas because of its flammability and low
window contamination. Equation 4 shows the chemical reaction of the
mixture
4C2 H2 10 O2 65N2 f 8CO2 4H2 O O2 65N2
4
where denotes the amount of excess oxygen. As the products of
combustion cool over a relatively long time (2 s) because of heat
transfer to the chamber walls, the pressure slowly decreased. The spray
injection begins when the pressure of the cooling burned mixture
reaches the preset conditions, as illustrated in Figure 2. The temperature,
density, and oxygen concentrations of the gas in the chamber at the time
of injection can be varied widely with this simulation procedure. The
camera was triggered to start the recording by the injection signal, and
the record duration was long enough to cover the whole spray,

Figure 2. Chamber pressure versus time, illustrating the method used

to generate experimental conditions simulating engine conditions.

combustion, and soot measurements. The exposure time was 3 s,

and the image interval was 66.5 s, for all test conditions.
For the experiments presented in this paper, dierent ambient
temperatures were considered for the spray, combustion, and soot
measurement ranging from 800 to 1200 K that covered both lowtemperature combustion and conventional combustion in a diesel
engine. The ambient temperature means the in-chamber temperature
at the start of injection, which was calculated from the premixed
combustion pressure at the time of injection. The ambient density was
kept constant at 14.8 kg/m3. Diesel combustion with 1000 K ambient
temperature, 21% oxygen concentration, and 14.8 kg/m3 ambient
density is a typical diesel in-cylinder environment with the piston at
top dead center (TDC). Two dierent volumetric blend fuels were used
in this study: one was the 20% butanol/80% soybean biodiesel blend
referred to as B20S80, and the other was the 20% ethanol/80% soybean
biodiesel blend referred to as E20S80. The physical and chemical
properties of soybean biodiesel, ethanol, butanol, and the blend fuels
are listed in Table 1. It can be found that the B20S80 fuel has a higher
cetane number and lower oxygen content compared to the E20S80 fuel,
while the density and heating values of B20S80 and E20S80 fuels only
have a slight dierence.

3. RESULTS AND DISCUSSION

3.1. Spray Images and the Potential Microexplosion.
Figure 3 demonstrates the spray image at 800 and 900 K ambient
temperatures. It can be observed that the tip of the spray jet
erupted into a plume and expanded the spray tip. Some droplets
moved away from the spray jet, and these droplets had a higher
evaporation rate, showing lower reflective light intensity. These
phenomena indicated that the microexplosion should be occurred at these experimental conditions. The microexplosion
phenomenon is caused by the volatility difference between the
additives (butanol or ethanol) and the base fuel (biodiesel). The
interior additives and base fuel become superheated as the
droplet is heated by convective and radiative heat transfer from
the surrounding ambient temperature. The superheat of liquid,
which is in the thermodynamically metastable condition, is
maintained as long as no phase transformation occurs within
the droplet. As the droplet temperature approaches the superheat
limit, the occurrence of bubble nucleation dominates, leading to
the internal formation of vapor bubbles, rapid evaporation, and
consequently, disintegration of the superheated liquid. The

Figure 3. Spray jet images for microexplosion at 800 and 900 K ambient temperature.
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Figure 4. Combustion pressure and heat release rate at dierent

ambient temperatures.

violent disintegration produces the momentum to disperse the

fine secondary droplets into a large physical volume and, consequently, enhances the fuel air mixing in the combustion field.
This has the potential to suppress the formation of soot and
unburned hydrocarbons.
The microexplosion in water and oil emulsied fuel has been
studied widely,42,43 but these studies just focused on a single
droplet with a diameter of about 1 mm. Few studies was found in
the literature about the microexplosion in a diesel spray from an
injector. In recent studies by Lee et al.44 and Shen et al.,45
microexplosions in mixtures of ethanol
biodiesel and butanol
biodiesel were studied using the numerical model proposed
by Zeng and Lee;46 however, there was no experimental validation in these papers. In this study, for the blend of B20S80 and
E20S80, the butanol or ethanol has a much lower boiling point
compared to biodiesel. Therefore, it was quite possible that a
bubble formed in the fuel droplet because of this drastic fuel
property dierence and nally incurred the microexplosion.
Furthermore, the fuel downstream of the jet atomized better
compared to upstream, as illustrated by Figure 3, indicating
downstream of the jet would be easier to reach the superheat
limit and to form bubble nucleation. However, when the ambient

ARTICLE

temperature increased (>900 K), all of the blended fuel vaporized very fast, resulting in no time to form bubble nucleation in
the blended fuels.
3.2. Combustion Pressure and Heat Release Rate Analysis.
Figure 4 presents the combustion pressure (averaged over 10
injections) and heat release rate with B20S80 and E20S80 at
different ambient temperatures. The combustion pressure is the
total pressure derived from the transducer minus the initial
ambient pressure at the time of injection. It should be noted
that the energy input was 3.83 and 3.69 kJ for B20S80 and
E20S80 fuels, respectively, and the energy difference was 3.65%
for these two blend fuels. Figure 4 shows that the combustion
pressure of the B20S80 fuel was lower than the E20S80 fuel,
although the B20S80 fuel had a little higher energy input because
of its higher heating value and density. The pressure rise is
directly proportional to combustion efficiency in constant-volume adiabatic combustion.47 However, the heat loss is inevitable
in a real constant-volume combustion chamber, and the magnitude of the heat loss is dependent upon a number of aspects, such
as flame area interacting with the chamber wall, flame radiation,
and the ratio of premixed and diffused combustion. A larger
flame
wall interaction area and higher flame temperature will
enhance both convection and radiation heat transfer through the
wall, causing higher heat loss. Meanwhile, a premixed dominant
combustion reduces the combustion duration and, correspondingly, reduces the time of heat transfer compared to mixing
controlled dominant combustion, resulting in a further increase
of the maximum combustion pressure. Therefore, the peak
pressure in this experiment can be regarded as an indication of
the heat release ability of the fuel under certain experimental
conditions rather than ideal constant-volume adiabatic conditions. It can be observed from Figure 4 that the E20S80 fuel had a
higher peak pressure compared to the B20S80 fuel, indicating a
potentially higher thermal efficiency of the E20S80 fuel. The
possible explanation of this observation is that less combustion
occurred near the wall region with E20S80, leading to lower heat
loss. Also, the higher latent heat for ethanol could result in a
lower flame temperature, leading to a lower flame radiation loss,
and a lower soot formation for E20S80 induced a lower flame
radiation loss. In addition, the laminar burning velocity of ethanol
is higher than that of butanol,48,49 thereby the E20S80 fuel had a
shorter combustion duration and less heat loss.
For the autoignition timing, it can be seen from Figure 4 that
the ignition delay became longer at a lower ambient temperature.
A longer autoignition delay allowed more time for ambient air to
be entrained into the jet to form a premixed zone with fuel vapor,
thereby more fuel was burnt by premixed combustion at a lower
ambient temperature. The heat release rate plots in Figure 4
demonstrate this transition from a mixing controlled combustion
at 1200 K to a premixed combustion dominant one at 800 K.
With regard to the fuel eects, Figure 4 demonstrates that the
autoignition delay for B20S80 was shorter than that of E20S80 in
the 1000 and 1200 K ambient temperature cases because of the
higher cetane number for B20S80. Meanwhile, the autoignition
delay for B20S80 and E20S80 was nearly the same at 800 K
ambient temperature, which can be explained by the fact that, at
the lower ambient temperature, the chemical reaction rate
reduced and weakened the eect of the chemical autoignition
delay because of the dierent cetane numbers, whereas the
physical delay because of higher volatility and lower viscosity
for the E20S80 fuel played a more important role on the
autoignition.
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Figure 5. Natural ame luminosity and soot distribution for E20S80

and B20S80 fuels at 800 K ambient temperature.

Figure 6. Natural ame luminosity and soot distribution for E20S80

and B20S80 fuels at 1000 K ambient temperature.

3.3. Natural Flame Images and Soot Formation Process.

Figures 5
7 demonstrate the natural flame luminosity and soot
measurement of B20S80 and E20S80 at various ambient temperatures. The time on the upper left corner represented the time at
which the image was captured, and the labels F and S on the
upper right corner represented flame emission and soot measurement, respectively. For natural flame and soot measurement, the
aperture was set to f/32 and f/4.5, respectively. The aperture is the
opening that determines the cone angle of a bundle of rays that
come to focus in the image plane. Some images that represented
different combustion and soot development phases were demonstrated in this section. It can be seen from Figure 5 that, for the
B20S80 fuel at 800 K ambient temperature, the flame was first
observed near the wall region at around 3.66 ms. Less air was
entrained to reach this region because of the ongoing combustion,
and as a consequence, there was a greater chance for soot generation
in this region, which was confirmed by the soot image at the same
time. Subsequently, the natural flame luminosity became brighter
(larger pixel intensity value), and the flame distribution became

larger at 4.85 ms. More soot was generated near the wall region at
the same time. In the following image, the diffusion flame propagated toward the injector but the intensive combustion was still
visible near the wall region because of a slow chemical reaction rate
at lower ambient temperature. Therefore, the soot distribution
could be observed near the wall region and downstream of the
spray jet. By 6.45 ms, the fading flame luminosity indicated that the
combustion had nearly completed in the chamber and the soot had
been oxidized mostly. In comparison to the B20S80 fuel, the natural
flame luminosity decreased for the E20S80 fuel, which is reasonable
because the flame temperature was reduced as a result of the higher
latent heat for ethanol. The soot was first observable downstream of
the spray jet at around 3.99 ms. Next, the flame propagated toward
the injector; less combustion occurred near the wall region; and the
soot distribution also moved toward the injector at 4.52 ms. After
4.52 ms, the main soot distribution region was in the reacting spray
jet. Finally, by 6.18 ms, the fading flame luminosity indicated that the
combustion had nearly completed in the chamber and the soot had
been oxidized mostly.
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Figure 8. Total soot mass for B20S80 and E20S80 fuels at dierent
ambient temperatures.

Figure 7. Natural ame luminosity and soot distribution for E20S80

and B20S80 fuels at 1200 K ambient temperature.

Figure 6 demonstrates the natural ame luminosity and soot

distribution of the B20S80 and E20S80 fuels at 1000 K ambient
temperature. The ame luminosity was brighter than that of
800 K ambient temperature because of the more intensive
combustion reaction. Only a little premixed combustion occurred, as shown in Figure 4; therefore, the diusion ame as well
as the soot emission could be seen downstream of the spray at
2.39 ms for B20S80 and E20S80 fuels. Subsequently, the ame
propagated to the chamber wall, and more regions began to
combust. Meanwhile, a higher soot concentration was perceivable near the wall region. For the B20S80 fuel, the ame
luminosity was observed near the wall region and downstream
of the spray jet after 3.46 ms; therefore, the soot was also
perceivable at these two regions. For the E20S80 fuel, however,
more combustion was detected downstream of the spray jet after
3.59 ms and there was little combustion ame near the wall
region. Therefore, the main soot distribution was also downstream of the spray jet.

Figure 7 demonstrates the natural ame luminosity and soot

distribution of the B20S80 and E20S80 fuels at 1200 K ambient
temperature. The ame luminosity was the brightest among
three ambient temperatures. No premixed combustion occurred,
as shown in Figure 4. The diusion ame can be observed much
earlier, and this initial diusion ame kernel was closer to the
injector. Correspondingly, the soot was also observed earlier than
those of 800 and 1000 K ambient temperatures, and the soot
distribution was also closer to the injector at 2.00 ms for B20S80
and 2.13 ms for E20S80. The ame then propagated downstream, and the main combustion occurred downstream of the
spray jet for B20S80 and E20S80 because of the fast combustion
reaction at 1200 K ambient temperature. Little combustion ame
was observed near the wall region for B20S80 and E20S80 fuels.
Therefore, the main soot distribution was also downstream of the
spray jet for B20S80 and E20S80 fuels.
From Figures 5
7, it can be found that the soot distribution
was altered with the increase of the ambient temperature. For the
B20S80 fuel, the main soot distribution was near the wall region
at 800 K ambient temperature, the soot distribution was reduced
near the wall region with the increase of the ambient temperature, and more soot was formed downstream of the spray jet at
1000 and 1200 K ambient temperatures. For E20S80 fuel, the
soot formation was also increased downstream of the spray jet
with the increase of the ambient temperature. As reported in
previous studies,32 the ame lift-o length decreases as the
ambient temperature increases. The shorter lift-o length resulted in less air entrained downstream of the spray jet, and thus,
more soot was observed at this region.
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Energy & Fuels

3.4. Total Soot Mass Analysis. Figure 8 shows the total soot
mass and the normalized time-integrated soot mass (NTISM) of
B20S80 and E20S80 fuels at three different ambient temperatures.
Time-integrated total soot mass was introduced because it considered not only the soot amount but also the soot existing time
within the flame. For a better comparison, all of the time-integrated
total soot masses were normalized by that of combustion at 800 K
ambient temperature with the B20S80 fuel. A single value of
NTISM was thus introduced to demonstrate the soot tendency to
get away from oxidation and appear in the exhaust pipe in a real
diesel engine, as shown in Figure 8b. As aforementioned, the energy
input for B20S80 and E20S80 fuels was 3.83 and 3.69 kJ, respectively. To eliminate the effect of different energy inputs, the value of
time-integrated total soot mass was divided by the energy input for
different fuel blends, which has also been shown in Figure 8b. It was
also demonstrated that the different energy inputs have little effect
on the value of NTISM.
As shown in Figure 8a, soot formation and oxidation demonstrated dierent behavior at dierent ambient temperatures for
both tested fuels. At a low ambient temperature of 800 K, a peak
value of total soot mass was observed, which clearly demarcated
the soot formation and oxidation process, while at high ambient
temperature, the soot formation dominated at the beginning of
the combustion and the total soot mass reached a quasi-steady
state during the combustion before it dropped to zero approaching the end of the combustion. The soot oxidation rate has been
illustrated with a gray dash line, which was dened as the slope
connecting between the peak value of the total soot mass and the
location where it rst dropped to zero. It can be found that the
soot oxidation rate was increased with the increase of the ambient
temperature. The net soot release is the competition results of
soot formation and oxidation. Although the lower ambient
temperature reduced the soot oxidation rate, the soot formation
rate had also been reduced because of the lower combustion
temperature. Because the soot formation was inhibited eectively
at lower ambient temperature, the total soot mass was reduced
with the decrease of ambient temperatures. Therefore, inhibition
of the soot formation was more important than acceleration of
soot oxidation at present experimental conditions.
As shown in Figure 8b, the value of NTISM was increased for
both tested fuels with the increment of ambient temperatures. At
higher ambient temperatures, less ambient air was entrained by
the spray jet because of the shorter ame lift-o and less fuel was
burnt by premixed combustion. The weak premixed combustion
with less ambient air entrainment resulted in some higher fuelrich zones, thus leading to higher soot formation. In comparison
to the B20S80 fuel, the E20S80 fuel had a lower value of NTISM
at all tested ambient temperature conditions and the reduction
was as much as 30
60% depending upon dierent ambient
temperatures. The reduction can be attributed by a number of
factors. First of all, the higher oxygen content of E20S8 compensating for the lack of air entrained in the ame resulted in
lower soot generation. Second, a higher volatility and a lower
viscosity for E20S80 fuel would improve the mixture formation
and reduce the local equivalence ratio favoring the soot exhibition. As a conclusion, the E20S80 fuel presented more advantages to reduce the soot emission compared to the B20S80 fuel.
Furthermore, increasing the ambient temperature from 800 to
1200 K led to a rapid increase in soot formation for B20S80 and
E20S80 fuels. Therefore, a lower environment temperature with
the piston at TDC should have more advantages to the combustion and soot emissions control for a real diesel engine.

ARTICLE

4. CONCLUSION
To investigate the eects of dierent alcohol additives in biodiesel
on the spray, combustion characteristics, and soot formation and
oxidation, a detailed comparative study between the butanol
biodiesel blend and the ethanol
biodiesel blend was carried
out in an optical constant volume combustion chamber. The
B20S80 (20 vol % butanol 80 vol % soybean biodiesel) and
E20S80 (20 vol % ethanol 80 vol % soybean biodiesel) fuels were
used as the test fuel at dierent ambient temperatures, ranging from
800 to 1200 K. The main conclusions are as following: (1) The
microexplosion occurred for the B20S80 and E20S80 fuels at 800
and 900 K ambient temperatures because of the volatility dierence
between the additives (butanol or ethanol) and the base fuel
(biodiesel). (2) The E20S80 fuel had a higher peak pressure
compared to the B20S80 fuel, indicating a higher potential thermal
eciency. Meanwhile, the E20S80 fuel had a shorter combustion
duration compared to the B20S80 fuel. (3) The autoignition was
earlier for the B20S80 fuel at 1000 and 1200 K ambient temperature
because of its higher cetane number. However, the autoignition of
the B20S80 and E20S80 fuels was nearly the same at 800 K ambient
temperature because the eect of chemical autoignition delay as a
result of the dierent cetane numbers was weakened, whereas the
physical delay because of a higher volatility and lower viscosity for
E20S80 had a larger eect on the autoignition. (4) The natural ame
luminosity was increased with elevated ambient temperatures. The
E20S80 fuel had a lower ame luminosity compared to the B20S80
fuel. (5) The soot distribution was increased downstream of the
spray jet at higher ambient temperatures. The E20S80 fuel had a
lower value of NTISM compared to the B20S80 fuel because of
its higher oxygen content, which can compensate for less air
entrained in the ame. In addition, a higher volatility, lower
viscosity, and lower cetane number improved the mixture formation
and reduced the local equivalence ratio. Therefore, the E20S80
fuel exhibited more advantages to reduce the soot emission
compared to the B20S80 fuel. (6) The total soot mass were
sensitive to the ambient temperature for both fuels, indicating that a
lower environment temperature near the TDC should be more
advantageous to the combustion and emissions control for a real
diesel engine because the soot formation can be inhibited and the
NOx emission can also be reduced as a result of the lower environment temperature, leading to lower combustion temperature.
AUTHOR INFORMATION
Corresponding Author

*Telephone: 1-217-333-5879. Fax: 1-217-244-6534. E-mail: cee@

illinois.edu.

ACKNOWLEDGMENT
The authors appreciate John Scheider and Jonathon McCrady
from the University of Illinois at Urbana
Champaign for their
help during the research. The help of the American Analytical
Chemistry Laboratories and Incobrasa Industries, Ltd. with the
fuel tests is also gratefully acknowledged. This work was supported in part by the U.S. Department of Energy (DOE) under
Grant DE-FC26-05NT42634, the DOE-sponsored Graduate
Automotive Technology Education (GATE) Centers of Excellence under Grant DE-FG26-05NT42622, and the China Scholarship Council under Project [2009]3012. This work was
performed using the equipment at the University of Illinois,
and the support of the university sta is greatly appreciated.
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