Fuel 133 (2014) 317325

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Fuel
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Time-resolved spray, ame, soot quantitative measurement fueling

n-butanol and soybean biodiesel in a constant volume chamber under
various ambient temperatures
Haifeng Liu a, Ming Huo b, Yu Liu c, Xin Wang a, Hu Wang d, Mingfa Yao a,, Chia-fon F. Lee b,e,
a

State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China

Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, IL 61801, USA
State Key Laboratory of Automobile Dynamic Simulation, Jilin University, Jilin 130012, China
d
Engine Research Center, University of Wisconsin-Madison, Madison, WI 53705, USA
e
Center for Combustion Energy, Tsinghua University, Beijing 100084, China
b
c

h i g h l i g h t s
 Liquid penetration length of n-butanol is less affected by the downstream ame.
 Flame propagation and distribution of n-butanol is less sensitive to temperature.
 Biodiesel soot concentrates on the reacting spray jet and near wall region.
 The soot of n-butanol is very low and concentrates on reacting spray at 900 K and 1000 K.
 B50D50 soot is lower 2030% than biodiesel at the same fuel oxygen content.

a r t i c l e

i n f o

Article history:
Received 7 January 2014
Received in revised form 18 March 2014
Accepted 14 May 2014
Available online 29 May 2014
Keywords:
n-Butanol
Soybean biodiesel
Constant volume chamber
Quantitative high time-resolved soot
measurement
Low temperature combustion

a b s t r a c t
The spray, ame natural luminosity and soot quantitative measurement by fueling n-butanol and soybean
biodiesel were investigated on a constant volume chamber using multi laser diagnostics with high temporal
resolution of 15,037 frames per second. The ambient temperature ranged from 700 K to 1000 K was applied
to mimic the diesel in-cylinder environment covering both conventional and low temperature combustion
conditions. Results demonstrate that the transient liquid penetration lengths gradually decrease with the
development of injection in a burning spray. The transient liquid penetration length of n-butanol is less
affected by the downstream ame and is shorter than that of biodiesel under similar conditions. The two
fuels also present drastically different ame dynamics and emission characteristics during the combustion
process. n-Butanol displays higher normalized combustion pressure indicating higher potential thermal
efciency. The ame can be observed at reacting spray jet and near wall region for biodiesel, while the main
n-butanol ame is concentrated on reacting spray jet. Compared to biodiesel, the ame luminosity of
n-butanol is lower and its propagation and distribution is less sensitive to ambient temperatures. Ambient
temperature is conrmed as the dominant impact on the soot emissions as the net soot increases for both
tested fuels with elevated ambient temperature. No soot emission is detected for either n-butanol or biodiesel at low ambient temperature of 700 K. The soot starts to appear at both downstream of the jet and near
wall regions from 800 K for biodiesel whereas the soot do not emerge until 900 K for n-butanol. The soot
concentration of n-butanol is also much lower and restricted within the downstream of the spray jet even
at high ambient temperatures. A particular interesting observation is that the normalized time integrated
soot mass for B50D50 (50% n-butanol and 50% low-sulfur diesel fuel in volume) is 2030% lower than that of
neat biodiesel fuel at different ambient temperatures even though the oxygen content in both fuels is nearly
the same. The higher soot formation for biodiesel is explained by the fact that fuel-bound oxygen is less
effective in reducing soot production and that higher viscosity and boiling point results in more local high
equivalence-ratio region in mixing process. In this regard, n-butanol is more effective in suppressing the
soot formation and shows stronger soot reduction capability than that of biodiesel.
2014 Elsevier Ltd. All rights reserved.

Corresponding authors at: State Key Laboratory of Engines, Tianjin University, Tianjin, 300072, China. Tel.: +86 22 27406832; fax: +86 22 27383362 (M. Yao), Department
of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, IL 61801, USA. Tel.: +1 217 3335879; fax: +1 217 2446534 (C.-f. F. Lee).
E-mail addresses: y_mingfa@tju.edu.cn (M. Yao), cee@illinois.edu (C.-f. F. Lee).
http://dx.doi.org/10.1016/j.fuel.2014.05.038
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

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H. Liu et al. / Fuel 133 (2014) 317325

1. Introduction
Bio-fuels have received increasing scientic and public attention due to the fact that they can reduce greenhouse gas emissions
and increase energy security and diversity. Among amounts of biofuels, biodiesel is the primary alternative fuel for diesel engines
because biodiesel properties are similar to the diesel fuel. Some
previous studies have shown that an engine fuelled with biodiesel
can reduce emissions of total hydrocarbons (THC), carbon monoxide (CO), and particulate matter. However, there is slightly increase
in brake specic fuel consumption and nitrogen oxides (NOx) emissions [19]. On the other hand, n-butanol is a very competitive
alternative to be applied in diesel engines and is getting popular
recently. Like ethanol, n-butanol is a biomass based renewable fuel
that can be produced by alcoholic fermentation of the biomass
feedstocks [10]. Fuel properties indicate that n-butanol has the
potential to overcome the drawbacks brought by ethanol in several
aspects, i.e. higher heating value, good intersolubility with diesel,
higher viscosity resulting in less wear problems, no corrosion to
the existing pipelines. Compared with biodiesel, n-butanol contains more oxygen content indicating stronger ability on soot
reduction. The viscosity of n-butanol is close to diesel fuel, while
biodiesel has relatively higher viscosity than diesel fuel, and thus
n-butanol is more suitable for diesel engine compared to biodiesel.
Some previous studies have shown that an engine fuelled with nbutanol can reduce emissions of soot, NOx and CO but slightly
increase brake specic fuel consumption and THC emissions, while
the thermal efciency increases slightly compared with diesel fuel
[1117].
Although many studies have been conducted on effects of biodiesel and n-butanol on combustion and emissions, these studies
are usually carried out on engine benches and focus on engine performance rather than on the fundamental aspects such as the
spray, ame development and soot distribution. It is difcult to
isolate the effects of basic parameters (e.g., in-cylinder gas temperature or pressure) associated with the combustion and soot formation based only on the engine tests. Meanwhile, the constant
volume chamber is often used to create well-characterized ambient environment for diesel spray combustion and has also been
used for biodiesel research in a number of studies. Wang et al.
[18,19] reported the spray, ame, and soot characteristics of biodiesels in a constant volume combustion chamber with different
injection pressures. The ambient temperature and pressure were
set to 885 K and 4 MPa to simulate the typical thermodynamic
condition in diesel engines. Nerva et al. [20] investigated the physical and chemical inuences of biodiesel on spray mixing, ignition,
combustion and soot formation in a constant volume chamber by
using a range of optical diagnostics at 900 K and 1000 K ambient
temperatures. These ambient conditions are typically encountered
in conventional combustion mode. Recently, Zhang et al. [21,22]
investigated the biodiesel spray combustion in a constant volume
chamber at lower ambient temperature of 800 K. In our previous
study [23], the combustion and soot emissions of n-butanol and
soybean biodiesel have been measured in a constant volume
chamber at different oxygen concentrations at 800 K and 1000 K.
However, 800 K is still not sufciently low to characterize the earlyinjection conditions in premixed charge compression ignition
(PCCI) and low temperature combustion (LTC). Literature survey
suggests little studies have been conducted regarding the biodiesel
combustion at ambient temperature lower than 800 K. It should
also be mentioned that soot emissions were not directly measured
in a burning spray plume in most of the aforementioned studies by
using two color thermometry [18,19,21,22]. Nerva et al. [20]
applied laser induced incandescence for soot measurement, yet
yielded low temporal resolutions for revealing the detailed soot
formation/oxidation mechanisms. In this respective, quantitative

high time-resolved soot measurement is a valuable supplement

to the current knowledge base on biodiesels combustion.
For n-butanol, extensive fundamental combustion works have
been conducted on both premixed and diffusion ames. The laminar ame speeds and ignition delays have been measured and low
temperature and high temperature kinetics have been proposed by
different research group at a wide range of temperatures, pressures
and equivalence ratios [2428]. However, to authors knowledge,
there is little studies on combustion and soot formation of n-butanol under a more real diesel engine condition where the ambient
pressure can reach up to 4 MPa upon auto-ignition and local equivalence ratio can exceed three or even higher. As a promising alternative fuel in diesel engines, the understanding of the spray, ame
and soot distribution for n-butanol under diesel combustion conditions is very crucial towards the application of next-generation
bio-fuels.
Based on literatures survey, it can be summarized that n-butanol
is a promising alternative in the future energy market for blending
with diesel, while biodiesel is the primary alternative for diesel
fuel in the present state. A detailed comparative study between nbutanol and biodiesel is important to promote their utilization in
diesel engines. Moreover, it is very crucial to acquire spray, combustion and soot characteristics for biodiesel and n-butanol under
lower ambient temperature because the advanced combustion
strategies such as PCCI and LTC will most likely be used on diesel
engines in the near future. The goal of the present study is to quantify the fundamental combustion process of neat n-butanol and
neat soybean biodiesel in a constant volume chamber at both conventional and LTC conditions by using multi optical diagnostics.
These results will be of great value for the numerical model validation, especially in view of the spray and soot models for bio-fuels.
Further, to compare the soot reduction capability between n-butanol and biodiesel, the B50D50 fuel (50% n-butanol, 50% low-sulfur
diesel fuel, in volume) was tested due to the same oxygen content
to biodiesel and the mechanisms on soot reduction were analyzed
based on the chemical kinetics and physical mixing processes. This
paper was also the further development on our previous works.

2. Experimental setup and procedures

The study was conducted in a constant volume chamber with a
bore of 110 mm and a height of 65 mm. A hydraulic-actuated electronic-controlled unit injector (HEUI Caterpillar HI300A) with 6
holes was mounted at the center of the chamber bottom. This
injector is adopted in the medium-duty engine with 7.2 l displacement and 110 mm bore size and the orice diameter is 0.145 mm.
The injector has a unique prime feature, which breaks the single
large injection charge into two separated injections. Before the
main injection, a small pilot injection can be produced to lower
the combustion noise. The injection pressure was 134 MPa and
the injection volume was 120 mm3 to simulate a high load fuel
mass. The detailed setup of constant volume chamber can be found
in previous studies [23].
A typical in-cylinder environment at top dead center in diesel
engines is 1000 K ambient temperature, 21% oxygen concentration
and 14.8 kg/m3 ambient density. To simulate the lower thermodynamic conditions in PCCI an LTC modes when the fuel injection
occurs, four different ambient temperatures were considered as
700 K, 800 K, 900 K and 1000 K, while the oxygen concentration
and ambient density was set to 21% and 14.8 kg/m3, respectively.
The fuels used in this work are listed in Table 1. Soybean biodiesel
denoted as S100 was bought from Incobrasa Industries Ltd. in the
United States and the detailed fuel properties can be found in previous studies [23]. The n-butanol denoted as B100 with 99.9% purity was used in the present study.

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H. Liu et al. / Fuel 133 (2014) 317325

Table 1
Fuel properties of ethanol, n-butanol, soybean biodiesel, and diesel fuel.

Properties

Ethanol

n-Butanol

Soybean biodiesel (ASTM)

Diesel (ASTM)

Molecular formula
Cetane number
Oxygen content (wt.%)
Density (g/ml) at 20 C
Autoignition temperature (C)
Flash point (C) at closed cup
Lower heating value (MJ/kg)
Boiling point (C)
Stoichiometric ratio
Latent heating (25 C kJ/kg)
Viscosity (mm2/s) at 40 C
Surface tension (N/m) at 20 C

C2H5OH
8
34.8
0.790
434
8
26.8
78.4
9.02
904
1.08
22.32

C4H9OH
25
21.6
0.81
385
35
33.1
117.7
11.21
582
2.63
24.6

CH3OOCR
51 (D 613)
10
0.887 (D 1298) at 15 C
363
173.9 (D 93)
37.53 (D 240)
342a (D 1160)
12.5
200
4.0 (D 445)
34.4

C12AC25
47.1
0
0.837
210
6588
42.5
180370
14.3
270
2.42
31.4

Note: The boiling point for soybean biodiesel is the distillation temperature 90% recovered.

The forward illumination light extinction (FILE) method developed and veried by Xu and Lee [29] was adopted to provide high
time-resolved quantitative information on the spatial and temporal distributions of soot. The FILE measurement has been successfully applied to the constant volume chamber to study transient
combustion, and yielded new insights in soot formation and
oxidation for diesel and other alternative fuels [2834]. The
current incident light for soot measurement was supplied by a
copper vapor laser (Oxford Lasers LS20-50), which has a pulse
repetitive frequency from 4.5 kHz to 20 kHz and each pulse lasts
2530 ns. The high speed camera (Phantom V7.1) with a 105 mm
focal length lens (Nikkor) was located above the chamber. The
camera and the laser were synchronized up to 15,037 frames per
second to produce high time-resolved measurement at resolution
of 256  256 pixels. The detailed setup for the soot measurement
can be found in previous studies [33,34].
Mie-scattering technique was adopted to study liquid jet penetration with the spray combustion. The set-up of liquid jet was the
same as FILE setup except there was no light diffuser behind the
jet. The interference lters were used to block the visible soot
luminosities to ensure only Mie scattering from liquid jet was
recorded. For the natural ame luminosity measurement, the diffuser and interference lters were removed and the laser light
was shut down. Flame images were directly obtained by the
camera with the same of time-resolved measurement as FILE.
The camera was triggered by the injection signal and the exposure
time for each frame was 3 ls.
3. Results and discussions
3.1. Spray liquid penetration length
Fig. 1 presents the evolution of liquid jet penetration using
n-butanol and biodiesel at different ambient temperatures. The
transient liquid penetration length is dened as the distance
between the injector orice and the pixel with intensity rst falling
below the preset threshold along the centerline of the liquid jet.
The similar method has been widely used in previous studies
[2,3,3537]. To reduce the cycle-to-cycle variation, the liquid penetration length is the average of over 5 injection cycles. The prime
character of the injector is evidenced from the early pilot-injection
from 1.33 ms to 1.53 ms after start of injection. The images of the
early pilot-injection can also been seen in Fig. 1(c). After 1.6 ms,
the main injection starts and the spray jet begins to penetrate into
the chamber rapidly and reaches its peak around 1.86 ms. Then,
the lengths reduce with the development of injection due to the
beginning of auto-ignition and subsequent ame propagation.
Finally, the injection nishes around 4.9 ms. Measurements of jet
penetrations without combustion have been widely studied in

Refs. [2,3,3537]. However, there is little report on liquid

penetration length under the combustion conditions. The spray
evolution in diesel engines is generally intervened by the combustion process due to the fact that ignition delay is typically shorter
than the injection duration. Therefore, the measurement of liquid
penetration length in a burning spray can complement the validation of spray model apart from the validation under conventional
without combustion conditions.
Fig. 1 also shows that the overall liquid penetration length
reduces with the increase of ambient temperature due to the fast
evaporation rate. At 700 K, the penetration length reaches quasisteady state and almost maintains at that value throughout the
entire injection duration, while a gradual decreasing trend is
observed at higher ambient temperatures. As shown in Fig. 4, the
earlier combustion ame at 700 K concentrates on the chamber
wall region, which is far from the spray and has little effect on
the spray development. However, the further increased ambient
temperature results in the higher combustion temperature and
the upstream ame is much closer to the injector, which can heat
the spray liquid and reduce the liquid penetration with the development of liquid spray as shown in Fig. 1(d). The spay images at
different ambient temperatures are shown in Fig. 1(e). It can also
be observed that the liquid spray changed into slimmer and shorter
at higher ambient temperature. Compared with n-butanol, the
liquid penetration length of biodiesel is longer under the same
ambient temperature due to less violent breakup during the atomization. As discussed by Lee et al. [3] and Park et al. [36], biodiesel
has higher viscosity, surface tension and evaporation temperature,
which results in the larger droplet and longer spray penetration
length. In addition, the penetration length of n-butanol has less
variation along the spray evolution compared to that of biodiesel,
i.e. the penetration length of n-butanol decreases from 16.8 mm
to 12.1 mm at 900 K, while the biodiesel decreases from 28.4 mm
to 13.2 mm. On one hand, n-butanol ame presents more downstream location of the spray jet. On the other hand, the decrease
of ame luminosity for n-butanol indicates the ame temperature
of n-butanol should be lower than that of biodiesel because the
ame luminosity is generally related to the combustion temperature. All of these make the ame had less impact on the liquid
penetration length of n-butanol.
3.2. Combustion pressure analysis
Fig. 2 presents the combustion pressures of n-butanol and biodiesel at different ambient temperatures. The combustion pressures are averaged over 10 injections. It shows that the
combustion pressure of n-butanol is lower than that of biodiesel.
The volumetric fuel ow rate is kept the same, whereas the biodiesel has higher density and heating value resulting in a higher

Liquid penetration length (mm)

H. Liu et al. / Fuel 133 (2014) 317325

Liquid penetration length (mm)

320

35
Ambient Temp.
700 K
800 K
900 K
1000 K

30
25
20
15
10
5
0

35
Ambient Temp.
700 K
800 K
900 K
1000 K

30
25
20
15
10
5
0

Time (ms)

Time (ms)

(a) n-Butanol (B100)

(b) Soybean biodiesel (S100)

(c) The early pilot-injection process for soybean biodiesel at 700 K

(d) Effect of flame on spray for soybean biodiesel at 800 K (left) and 1000 K (right)

Ambient temperature

700 K

800 K

900 K

1000 K

Soybean biodiesel

n-Butanol

(e) Spray images at different ambient temperatures

Fig. 1. The evolution process of liquid penetration length with combustion.

energy input. Therefore, the peak pressure is expected to increase

for the biodiesel. Moreover, the combustion process has a higher
pressure at lower ambient temperature except the biodiesel combustion pressure at 700 K. This is because the lower ambient temperature results in longer ignition delay as shown in Fig. 3, causing
more premixed combustion in chamber and consequently
increases the pressure. Furthermore, less heat loss through both
chamber wall conduction and ame radiation at low ambient temperature can also help to increase the pressure.
The total pressure rise reects combustion efciency in constant-volume adiabatic combustion. However, the heat loss caused
by both convection and radiation heat transfer through the wall is
inevitable in a real constant volume combustion chamber. Therefore, the peak pressure in this experiment is an indication of the
real heat release ability of fuels or the potential thermal efciency
as the previous discussions [23]. To compare the combustion peak
pressure between n-butanol and biodiesel, the effects of input

energy should be eliminated. Thus, the normalized peak pressure

(NPP) is introduced as follows:

NPP

pf Es

ps Ef

where pf is the peak pressure of tested fuels, ps is the peak pressure

of biodiesel at 1000 K ambient temperature. Es and Ef are the energy
input for biodiesel and tested fuels, which is calculated by
E = qVQLHV, where q, V, and QLHV represents the density, volume,
and low heating value, respectively. Fig. 3 shows that n-butanol
has a higher NPP value compared with biodiesel at different ambient temperatures, indicating higher potential thermal efciency.
The possible explanation is that less combustion occurs at near wall
region as shown in Fig. 4, leading to lower heat loss from the ame/
wall interaction. In addition, lower net soot can also contribute to
the lower radiation loss. The NPP of n-butanol at 700 K is 20% higher
than that of biodiesel at 1000 K, demonstrating that a proper fuel

Combustion Pressure (MPa)

H. Liu et al. / Fuel 133 (2014) 317325

1.5
1.2
0.9
0.6
0.3
0.0

700 K

900 K

S100
B100

1.5
1.2
0.9
0.6
0.3
0.0

Peak Value

Peak Value

PS100=1.51

PS100=1.44

PB100=1.39

PB100=1.27

800 K

1000 K
Peak Value

Peak Value

PS100=1.53

PS100=1.42

PB100=1.34

PB100=1.22

9 1

Time (ms)
Fig. 2. Combustion pressure at various ambient temperatures.

1.5

B100

NPP

1.2

S100

0.9
0.6

Auto-ignition Delay (ms)

0.3
0.0
3.2

B100
S100

2.8
2.4
2.0
1.6
700

800

900

1000

Ambient Temperature (K)

Fig. 3. Normalized peak pressure and auto-ignition delay at various ambient
temperatures.

property and lower ambient temperature will potentially result in

higher combustion thermal efciency for a real diesel engine. Strategies such as the heavy cooling EGR, Miller cycle with variable valve
timing, lower compression ratio can all contribute to the reduced
charge-gas temperature and accordingly improve the thermal efciency to some extent.
Regarding the auto-ignition timing, it becomes signicantly
retarded at lower ambient temperature regardless of the fuel as
shown in Fig. 3. As for the fuel effects, Fig. 3 demonstrates that the
auto-ignition delay for biodiesel is shorter than that of n-butanol
in all cases. The auto-ignition temperatures are similar for both
tested fuels but the biodiesel has a higher cetane number. However,
with the increase of the ambient temperature, the effect of fuel property on the auto-ignition delay difference becomes less apparent and
the auto-ignition delay is nearly the same at 1000 K for both fuels.
Also, a dramatic increase in auto-ignition delay is observed at
700 K, while the other higher ambient temperature cases manifest
a linear relation, indicating the non-linear behavior of the ignition
timing particularly at low ambient temperature.
3.3. Flame propagation and soot distribution
Fig. 4 demonstrates the natural ame luminosity and soot distribution of n-butanol and biodiesel at various ambient temperatures. The aperture was set to f/32 for all ame images except

321

the n-butanol fuel at 700 K with f/16 setting, which was due to
the much lower ame luminosity for n-butanol. For soot measurement, the aperture was set to f/4.5 for all conditions. The ame
luminosity is extremely weak at 700 K, and no soot is detected
for both fuels. On one hand, the lower ambient temperature results
in the longer ignition delay, and thus reduce the local equivalence
ratio. On the other hand, the lower ambient temperature results in
the lower ame temperature. All of these can suppress the soot
formation. The main combustion of both fuels rstly occurs at near
wall region and follows by the ame propagating towards the
nozzle. Since no soot can be observed, the ame should be from
the chemiluminescence due to the combustion of gas phase
hydrocarbon species.
As the ambient temperature increases, the ame difference
between n-butanol and biodiesel becomes more pronounced. At
800 K, the ame luminosity of n-butanol is still very weak and
no soot is detected at this condition. For biodiesel, the ame
appears at near wall region rst and the soot is accordingly formed
at 3.06 ms. The diffusion ame and the soot distribution propagate
in the same direction towards the nozzle at about 3.99 ms. Subsequently, the diffusion ame and soot are seen at near wall region
and within the reacting spray jet. As the diffusion ame propagates
towards the nozzle, more soot can be observed at the reacting
spray jet due to the continuously replenished fuel-rich regions at
the spray tip. At 900 K, the ame propagation and soot distribution
for biodiesel are similar to those of 800 K, while the early ame
development for n-butanol is similar to that of 800 K but the soot
located at downstream of spray jet is seen at the later combustion
phase at 900 K.
At 1000 K, the ame and soot formation for n-butanol is still
weak and rst observed at near wall region at 2.79 ms. Following
the ame propagation towards the nozzle, stronger ame luminosity and a small amount of soot is seen at the reacting spray jet. For
biodiesel, more vigorous diffusion ame and soot distribution can
be seen at downstream of the spray in contrary to the low ambient
temperature cases which locate at near wall region. Subsequently,
the ame propagates to the chamber wall and higher soot concentration is perceivable. In the following images, the ame and soot
distribution is seen at the reacting spray jet and near wall region.
The ame luminosity is reduced with the decrease of ambient
temperatures indicating a lower ame temperature. As the NOx is
strongly dependent on the ame temperature, the combustion of
n-butanol is expected to yield less NOx although the energy input
is a little different in this experiment. Previous studies have
reported less NOx emissions with n-butanol addition in diesel
engines [11,12], which support the observation in the current
study. Apart from the lower overall ame natural luminosity, less
natural ame is seen for n-butanol at near wall region in the later
combustion phase compared to biodiesel, which potentially
improve the thermal efciency due to less convective heat loss. A
higher vaporization rate resulted from lower boiling point of nbutanol causes faster combustion rate, and the main reaction zone
barely reaches the chamber wall. The soot mass for n-butanol is
very low at 900 K and 1000 K and no soot can be seen at 700 K
and 800 K, whereas for biodiesel, the wider soot distribution and
higher concentration is seen at the reacting spray jet and near wall
region from 800 K to 1000 K.
3.4. Total soot mass analysis
Fig. 5 presents the spatial integrated total soot mass at different
ambient temperatures for both fuels. The total soot mass is the
competition results of soot formation and oxidation. As shown in
Fig. 5, soot mass increases sharply and reaches a quasi-steady state
before it commences continual decline dropped to zero approaching the end of combustion. With the decrease of ambient

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H. Liu et al. / Fuel 133 (2014) 317325

B100 700K

S100 700K

Flame

Flame

B100 800K
Flame

B100 900K
Flame

S100 800K
Flame

S100 900K
Soot

Flame

B100 1000K
Soot

Flame

Soot

S100 1000K
Soot

Flame

Soot

Fig. 4. Natural ame luminosity and soot distribution at various ambient temperatures.

temperature, reduced total soot mass, retarded soot forming time

and shortened soot duration are observed. Compared with biodiesel, n-butanol has much lower total soot mass, which is because
n-butanol has larger oxygen content. On the other hand, a higher
volatility and a lower viscosity of n-butanol will improve the
mixture formation and reduce the local equivalence ratio.
To further reveal the potential of n-butanol on soot reduction,
B50D50 (50% n-butanol, 50% low-sulfur diesel fuel, in volume)
was tested. Fig. 5b shows that the B50D50 has the later soot formation timing and lower total soot mass compared to S100 even
though the oxygen content in both fuels is nearly the same
(10 wt.%), which indicates that the soot reduction capability is

not solely decided by the oxygen content. When comparing the

fuel properties, the chemical property between n-butanol and
biodiesel is apparently different as the oxygenated structure for
n-butanol and biodiesel are alcohol and ester, respectively. The
benecial effect of oxygenated fuels on soot emissions is often
credited to the enhanced carbon trapping into non-shooting
species (e.g., partially oxidized C1AC2 hydrocarbons) [38]. In other
words, fewer carbon atoms are available to mature into soot
precursors (e.g., ethylene, acetylene) after chemically bonding with
oxygen in the fuel. In many studies of oxygenated fuels, each
oxygen atom is connected to two carbon atoms tend to yield the
lowest soot emissions [3941]. This is easy to understand that in

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H. Liu et al. / Fuel 133 (2014) 317325

B100-800K
B100-900K
B100-1000K
S100-800K
S100-900K
S100-1000K

120
90
60
30
0
1

150

Total Soot Mass (g)

Total Soot Mass (g)

150

B50D50-800K
B50D50-1000K
S100-800K
S100-1000K

120
90
60
30
0
1

Time (ms)

Time (ms)
(a) The neat n-butanol and biodiesel

(b) The diesel/n-butanol blend and neat biodiesel

Fig. 5. Total soot mass at various ambient temperatures.

alternative distributions, an oxygen atom may trap only one (C@O)

or one-half (OACAO) of a carbon atom instead of up to two
(CAOAC) carbon atoms in the preferred embodiment [38].
Chemical kinetic studies of methyl decanoate have shown that
CO2 formation is signicant during low temperature combustion
region [42]. At low temperatures, the importance of CO2 formation
through the hydrocarboxyl radical (OCHO) and the methoxy
formyl radical (CH3OCO) as following:

OCHOM H CO2 M

R1

CH3 OCO CH3 CO2

R2

These kinetic reactions have been observed for methyl esters

group combustion including methyl decanoate and methyl butanoate [4247]. Obviously, two oxygen atoms in methyl esters can
only remove one carbon atom due to the formation of CO2, therefore the fuel-bound oxygen is less effective in reducing soot
production. Further, Osmont et al. [48,49] have also provided
explanation for the CO2 phenomenon based on bond energies. They
evaluated thermodynamic parameters and bond dissociation energies using quantum chemistry methods and found that the breaking of carbon oxygen bond was in general energetically
unfavorable compared to carbonAcarbon bond breaking. For
example, the lowest bond dissociation energy in methyl palmitate
for a CAO bond was approximately 89 kcal/mol, while the lowest
bond dissociation energy for a CAC bond in methyl palmitate
was reported at 83 kcal/mol. This observation provides a basis for
observations of methyl ester decomposition, where CO and CO2
are formed ostensibly as a result of carbon and oxygen remaining
bonded throughout the combustion process [47]. The most important is that the CO2 formation can also be measured in engine and
jet stirred reactor experiments [50,51]. The Szybist et al. [50] has
reported that the amount of fuel carbon converted to CO2 during
low temperature heat release (LTHR) is 69% by using methyl
decanoate on a motored engine. However, there is no CO2 can be
measured for the conventional diesel fuel or n-heptane. The oxidation of COCO2 does not take place under low temperature conditions when hydrocarbons are present [52]. Thus, the occurrence of
CO2 in LTHR regime shows that decarboxylation of ester groups
occurs during LTHR. One may argue that cetane number can also
have effect on combustion and soot emissions in diesel engines
in previous studies [17,40,53]. The lower cetane number results
in the longer ignition delay and thus can improve the mixing process of fuel and air and reduce the rich-fuel region. However, the
difference of ignition delay between B50D50 and S100 is almost
negligible under the current conditions. Therefore, the effects of
cetane number on combustion and soot emissions should not be
the main impact factor.
In addition to the chemical properties, fuel physical properties
are also different between n-butanol and biodiesel, which can

Fig. 6. The vapor-phase distribution of equivalence ratio for the diesel/n-butanol

blend and neat biodiesel at 1000 K ambient temperature.

Table 2
The normalized time integrated soot mass at various ambient temperatures.
Fuels

700 K

800 K

900 K

1000 K

S100
B50D50
B100

0
0
0

9.9
6.79
0

15.32
12.46
0.27

19.15
14.38
1

result in the different combustion process and soot emissions.

The boiling point, viscosity and surface tension of n-butanol are
lower than those of biodiesel. Therefore, the use of n-butanol can
improve the liquid jet atomization and mixing process and more
air should be entrained into the B50D50 in mixing processes and
consequently reduce the local fuel/air equivalence ratio. Fig. 6

324

H. Liu et al. / Fuel 133 (2014) 317325

shows the vapor-phase distribution of equivalence ratio for

B50D50 and biodiesel at 1000 K ambient temperature, which are
derived from the CFD simulation using the KIVA 3v-r2. It can be
found that the S100 has larger fuel-rich regions compared to the
B50D50. The higher boiling point, viscosity and surface tension
make the biodiesel fuel much harder to be atomized and mixed
with the ambient air than that of B50D50 fuel and it needs a longer
time to reach the wall for biodiesel. Therefore, a quite high equivalence-ratio region is formed at the downstream of spray jet. Further, the continuously replenished fuel-rich regions are penetrated
into chamber, and thus forms quite higher soot emissions.
It should also be mentioned that the soot formation timing is
retarded for B50D50. Soot precursors are generated during premixed reaction zone and these precursors can form soot as they
travel along with the spray jet. As the B50D50 fuel is used, more
ambient oxygen and fuel oxygen reacts with the precursors before
they have time to consolidate into soot. Table 2 shows the normalized time integrated soot mass (NTISM) of tested biofuels at different ambient temperatures. Time integrated total soot mass is equal
to the area inside the loop of total soot mass, which is introduced
because it considered not only the soot amount, but also the soot
existing time within the ame. Furthermore, the effects of input
energy in various biofuels are eliminated and all values are normalized. With the value of NTISM, it demonstrates the soot tendency to potentially appear in exhaust pipe in a real diesel
engine, meaning that higher NTISM value will result in larger soot
emissions. The specic NTISM is illustrated in Table 2 and this
value is again the average of over 5 injection cycles. An obvious
trend is that increasing the ambient temperature from 700 K to
1000 K leads to an increase in the value of NTISM for a given fuel.
The NTISM of biodiesel is much higher than that of n-butanol over
a wide range of ambient temperatures. In addition, with the similar
fuel oxygen content, the value of NTISM for B50D50 is lower 20
30% than that of S100 at different ambient temperatures without
the input energy effects. Therefore, it can be concluded that the
addition of n-butanol has larger soot reduction capability than that
of biodiesel under the same oxygen content and over a wide range
of ambient temperatures.
4. Conclusions
Neat n-butanol and neat soybean biodiesel were tested on a
constant volume combustion chamber. The spray, combustion
and soot evolution were measured using Mie scattering, combustion pressure analysis, natural ame luminosity and forward
illumination light extinction methods. Various ambient temperatures covering 700 K and 1000 K were tested to mimic the diesel
in-cylinder environment at both conventional and low temperature combustion conditions. The main conclusions are as
following:
(1) The transient liquid penetration lengths gradually decrease
with the development of injection under spray combustion
conditions because the liquid spray has faster evaporation
with the ame propagation. Such decreasing trend becomes
less apparent at 700 K regardless of the fuel. The transient
liquid penetration length of n-butanol is less affected by
the downstream ame and is shorter than that of biodiesel
under similar conditions.
(2) The ignition delay of the tested fuels presented non-linear
behavior as a much dramatic increase in auto-ignition delay
is observed at 700 K other than higher ambient temperatures. The auto-ignition delay difference between n-butanol
and biodiesel becomes less apparent with increasing of
ambient temperature. The combustion has a higher pressure

(3)

(4)

(5)

(6)

at lower ambient temperature except for biodiesel combustion pressure at 700 K. The n-butanol has a higher normalized peak pressure indicating a higher potential thermal
efciency.
For biodiesel, the combustion occurs at downstream of spray
jet at 1000 K, while the ame is rstly seen at near wall
region at lower ambient temperatures. For n-butanol, the
main combustion rstly occurs at near wall region followed
by the ame propagating towards the nozzle. The ame can
be seen at reacting spray jet and near wall region for biodiesel, while the main n-butanol ame concentrates on reacting
spray jet. Flame propagation and distribution for n-butanol
is less sensitive to ambient temperature and ame luminosity is lower compared to biodiesel ame.
The soot mass increases with elevated ambient temperature.
No soot is detected for n-butanol and biodiesel at 700 K. For
biodiesel, the wider soot distribution and higher concentration is seen at the reacting spray jet and near wall region
from 800 K to 1000 K. For n-butanol, no soot is seen at
800 K and very low soot is seen concentrating at the reacting
spray jet at 900 K and 1000 K.
The B50D50 (50% n-butanol and 50% low-sulfur diesel fuel in
volume) has the later soot formation timing and the lower
total soot mass compared to neat biodiesel although the
oxygen content in both fuels is nearly the same. The value
of normalized time integrated soot mass for B50D50 fuel is
lower 2030% than that of biodiesel at different ambient
temperatures. The higher soot formation for biodiesel is
due to the fact that fuel-bound oxygen is less effective in
reducing soot production and that higher viscosity and boiling point results in more fuel-rich regions in mixing process.
Overall, n-butanol is more effective in soot suppression and
presents higher thermal efciency under a wide range of
ambient temperature conditions.

Acknowledgments
The authors would like to acknowledge the nancial supports
provided by National Natural Science Foundation of China through
its Project of 51206120 and 51320105008 and by the U.S. Department of Energy through its Project of Grant DE-FG26-05NT42622.
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