Applied Energy 185 (2017) 519–530

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Ignition and combustion characteristics of n-pentanol–diesel blends in a

constant volume chamber
Yinjie Ma, Sheng Huang, Ronghua Huang ⇑, Yu Zhang, Shijie Xu
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

h i g h l i g h t s

 Fuel’s ignition and combustion characteristics are measured by different method.

 Diesel blends containing 20% and 40% n-pentanol are examined.
 D60P40 advances ignition phase over D80P20 under low oxygen content conditions.
 Flame luminosity is reduced with the increase of pentanol ratio in most conditions.
 Pentanol could significantly accelerate soot oxidation under all conditions.

a r t i c l e i n f o a b s t r a c t

Article history: Pentanol is considered as one of the most promising alternative biofuels due to its excellent physico-
Received 13 August 2016 chemical properties. The objective of this work was to compare the ignition and combustion character-
Received in revised form 18 October 2016 istics of different n-pentanol/diesel blends in an optical constant volume combustion chamber. The tested
Accepted 1 November 2016
fuels included 20% (D80P20) and 40% (D60P40) of n-pentanol blended with diesel in volume, and pure
Available online 8 November 2016
diesel (D100). Broadband chemiluminescence technique was used to measure the timing and location
of spray ignition. A high-speed CCD camera with two ND8 dimmer lenses was used to capture the incan-
Keywords:
descence radiated from the soot particles during combustion. A wide range of experimental conditions
Pentanol/diesel blends
Constant volume combustion chamber
was investigated. The ambient temperature ranged from 800 K to 1200 K and the oxygen concentration
Ignition characteristics ranging from 10% to 21%, covering both the conventional and low temperature combustion regimes. The
Flame lift-off length results show that pure diesel has shorter ignition delay and distance comparing to pentanol blends. A lar-
Natural flame luminosity ger blending proportion of pentanol D60P40 advances the ignition phase more than the D80P20 in low
oxygen concentration conditions. Due to the fuel-borne oxygen and the dilution effect, the natural flame
luminosity is reduced significantly with the increase of pentanol ratio in most conditions except under
the intermediate temperature region of 1000 K. In that condition, the shorter ignition delay and flame
lift-off length of pentanol blends cause a slightly increase in the natural flame luminosity. The natural
flame luminosity images showed that the oxygen-contained structure of pentanol could accelerate soot
oxidation under all conditions. This indicates that pentanol blends could decrease final soot emissions in
internal combustion engines.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction biofuels have obtained growing interest worldwidely as alterna-

tives or supplements in mobile vehicles due to their potential of
Diesel engines are widely used in modern transport, power gen- improving energy security and reducing pollutant emissions
eration, agriculture and irrigation systems due to their high ther- [7,8]. Biofuels are composed of or produced from biological raw
mal efficiency [1–6]. However, the high NOx and soot emissions materials, and mostly environment-friendly. Besides, biofuels also
and the fast depletion of fossil fuel resource greatly limit the devel- help reduce the carbon dioxide emissions [9], which can contribute
opment of diesel engines due to the recent rigorous regulations on to the domestic and international targets of greenhouse gas reduc-
pollutant emissions and fuel consumption. In the last two decades, tion. Therefore, many countries have established corresponding
policies to advocate the use of renewable biofuels for petroleum-
based ones. For example, Renewable Fuel Standard (RFS) program
⇑ Corresponding author.
[10] was proposed by the U.S. government and the 2030 Frame-
E-mail address: [email protected] (R. Huang).

http://dx.doi.org/10.1016/j.apenergy.2016.11.002
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.
520 Y. Ma et al. / Applied Energy 185 (2017) 519–530

work for climate and energy [11] was put forward by the EU tigating the ignition and combustion characteristics of fuels using
Commission. engine experiments may be not a good choice. Out-of-engine opti-
Among all the alternative fuels, short-chain alcohol-based bio- cal experiments can provide valuable information for understand-
fuels, such as methanol and ethanol, have received significant ing combustion process [41–43]. Optically accessible constant
attention due to their mature production technology and high oxy- volume chamber is a powerful tool to reproduce the ambient con-
gen content [12,13], which could effectively improve the combus- ditions relevant to thermal engines with good repeatability [44].
tion characteristics and reduce the soot emissions [14]. However, The main parameters such as temperature, gas density and oxygen
the low cetane number, high latent heat of vaporization, miscibility contents can be adjusted easily. With corresponding visualization
and stability problems when blended with diesel fuel greatly limit techniques such as high-speed schlieren imaging [45] and PLIF
the application of short-chain alcohols as alternative fuels for die- [46], the ignition and combustion processes of fuel sprays into
sel engines [15]. Long-chain alcohols containing four or more car- engine-likes conditions could be recorded. A few works were con-
bons have significant advantages over short-chain alcohols when ducted to investigate the effect of alcohol addiction on the ignition
using in diesel engines. Long-chain alcohols have higher energy and combustion characteristics of diesel spray in engine-like con-
density and higher cetane number than short-chain alcohols. They ditions. Liu [47] investigated the flame propagation and soot for-
also present better blend stability and could be blended with diesel mation of n-butanol/biodiesel/diesel blends in a constant volume
in large blend ratios. Moreover, less hygroscopic nature of higher combustion chamber. The results showed that low n-butanol addi-
alcohols makes it easier to store and transport [16]. Butanol is a tion had limited or no effect on the auto-ignition timing. Wu [48]
four-carbon alcohol and has been widely investigated as an alter- investigated the combustion characteristics of acetone-butanol-
native fuel or fuel additive in recent years [17,18]. Experimental ethanol (ABE) – diesel blends and found that the natural flame
studies on the engines fueled with butanol-diesel blends showed luminosity was reduced significantly with the increase of ABE ratio
that lower exhaust emissions could be achieved with slight impact and ABE50 achieved a shorter ignition delay. However, to the best
on engine performance [19–21]. Butanol also showed a good of the authors’ knowledge, there are still lack of reports on the igni-
exhaust gas recirculation (EGR) tolerance due to its oxygen- tion and combustion characteristics of pentanol-diesel blends.
containing structure, and a simultaneous reduction of smoke and Since the physical and chemical properties of long-chain alcohols
NOx emissions could be achieved while combining with the proper are quite different from that of neat diesel and other shorter alco-
EGR ratio and injection strategy [22,23]. hols, it is worthwhile to understand how the long-chain alcohol
Pentanol, a long-chain alcohol with five-carbon structure, has influences the ignition and combustion process of blends.
attracted much attention recently and is regarded as a most poten- In the present paper, an extensive investigation was conducted
tial next-generation biofuel. Pentanol can be produced from bio- on the ignition and combustion characteristics of higher alcohol
logical pathways like natural microbial fermentation of pentanol/diesel blends and conventional diesel fuel. The constant
engineered micro-organisms [24] and biosynthesis from glucose volume chamber was used to simulate the in-cylinder condition
[25]. Compared to butanol and other short-chain alcohols, pen- prior to injection in a real diesel engine. A wide range of experi-
tanol has higher energy density higher, larger cetane number, bet- mental conditions was investigated. The ambient temperature ran-
ter blend stability and less hygroscopic nature. These advantages ged from 800 K to 1200 K and the oxygen concentration ranged
make pentanol very competitive as an alternative fuel in diesel from 10% to 21%. The different ambient temperature represents
engines. By now, a few works on pentanol have been carried out different operating conditions of a real engine, while the different
in compression ignition engines [22,26–32]. It was found that n- oxygen level represents different EGR ratios were adopted. At the
pentanol blends had an obvious advantage over neat diesel fuel instant prior to injection, 800 K is the typical in-cylinder tempera-
in reducing the nitrogen oxides emissions, particulate mass and ture in the low temperature combustion (LTC) engine while 1200 K
number concentration, and increasing the brake thermal efficiency stands for the highest in-cylinder temperature in a traditional
[21,30,32]. Li et al. [31] used pure pentanol in a single-cylinder heavy duty diesel engine. 10% oxygen content is roughly equiva-
direct-injection diesel engine. The results showed that NOx and lent to the oxygen content in the cylinder of diesel engines with
soot emissions decrease significantly for pentanol with comparable 50% EGR rate, while 21% oxygen content is equivalent to the oxy-
efficiencies under single injection strategy without EGR. Kumar gen content in the cylinder of diesel engines without EGR. These
et al. [22,29] recently applied the combination of pentanol/diesel conditions represent the in-cylinder conditions prior to injection
blends and a medium EGR rate (20–30%) to achieve simultaneous in a real diesel engine with both traditional and LTC technology.
reduction of NOx and smoke emissions. The results showed that By using two target-oriented optical techniques, the detailed igni-
45% pentanol/diesel blends could be used in diesel engines without tion and combustion information were systematically analyzed for
any modifications, and would not cause any visible damage to the pentanol blends and pure diesel, such as ignition time, ignition
engine parts subject in long-term durability tests. Fundamental position, flame luminosity and flame lift-off length. Compared to
experimental [33–35] and kinetic modeling studies [36–38] for the short-chain alcohol blends, the results revealed a more com-
pentanol combustion were conducted to help understand and plex influence mechanism of ignition and combustion for higher
improve the efficient and clean application in diesel engines in alcohol pentanol/diesel blends, which is highly depended on the
the view of combustion chemistry. ambient conditions. The reported work expanded the understand-
The ‘‘diesel conceptual model” presented by Dec [39] and Mus- ing of high pentanol/diesel blends combustion and provided
culus [40] shows that the combustion process in diesel engine is a detailed experimental data to promote the application of the
complex process involving fuel atomization, vaporization, fuel-air new-generation biofuel in diesel engines.
mixing, ignition and combustion. They also confirmed that ignition
and combustion characteristics of fuel spray are the key factors
influencing the working performance and pollutant emission of 2. Experimental setup
diesel engines. Moreover, the experimental data on the ignition
and combustion processes are indispensable to develop the com- 2.1. High pressure chamber and injection system
bustion mechanism of fuels and validate the simulation results of
computational fluid dynamic models. However, since it is difficult A premixed combustion heated constant volume combustion
to control the environment and make observations due to the bomb (CVCB) was used to simulate the in-cylinder conditions of
cycle-by-cycle variations and the complex engine geometry, inves- a diesel engine at the time of injection. The schematic of the exper-
 Y. Ma et al. / Applied Energy 185 (2017) 519–530 521

imental setup is shown in Fig. 1. The major structure of the vessel The reliability and repeatability of spray and combustion experi-
is a symmetric cube with 380 mm sides and combustion chamber ments have been validated in our previous studies, and the maxi-
is a cube with edge length of 136 mm. The maximum penetration mum deviation was less than 5%. More information about the
of free spray is 120 mm, which meets the requirements of fully verification procedure can be found in Refs. [41,52,53].
developed spray combustion studies. To provide an optical access
for visualization, two quartz windows with a thickness of 50 mm
2.3. Optical techniques and processing methods
were installed in line with the light beam. Meanwhile, heating
sheets covered by insulating layers were adhered on the CVCB
Two different optical techniques were used to visualize the
body’s surfaces. The wall temperature of the combustion chamber
spray ignition and combustion processes. Broadband chemilumi-
at 383 K for all test conditions by a PID controller. The variation in
nescence technique was used to directly measure the location
chamber temperature is below 1 °C. The purpose is to prevent
and timing of spray ignition, which was introduced and validated
water vapor condensation on quartz windows and ensure the accu-
by Lillo et al. [54]. A high-speed CCD camera with two ND8 dimmer
racy of the intake process.
lenses was used to capture the incandescence radiated from the
A Bosch model CRIN2 fuel injector was used and installed verti-
high-temperature soot particles, which had been applied by Wang
cally in the center of a main port of the CVCB. It had a single sac-
et al. [53] and Huang et al. [52] recently. The camera settings for
type nozzle located on the injector axis. The orifice diameter mea-
the two of the imaging techniques are listed in Table 3.
sured by a microscopic was 0.234 mm. The injection process was
Broadband chemiluminescence imaging setup used a 600-nm
triggered and maintained for 2.5 ms by an electrical control unit
low-pass filter to reject higher wavelength thermal emission from
(ECU). An oil bath temperature control system was used to stabi-
species and later soot incandescence, while permitting collection
lize and adjust the temperature of the injector and fuel. The fuel
of other radicals (e.g. CH⁄, C2⁄). As shown in Fig. 2, the maximum
temperature was set as room temperature (298 K) in this work.
luminosity intensity inside the region of interest (the flame lift-
off length region) is plotted against time for a typical spray com-
2.2. Fuels and test matrix
bustion condition. The intensity increases from weak chemilumi-
nescence of cool-flame to intense glow by orders of magnitude. It
In the present study, n-pentanol (CAS No: 71-41-0) with a pur-
stabilizes at a certain level defined as high-temperature chemilu-
ity of 98% (analytical grade) was procured from China National
minescence level. Then we choose 50% intensity of the high-
Pharmaceutical Group Corporation. The commercial 0# diesel fuel
temperature chemiluminescence level as the ignition threshold.
was purchased from PetroChina Co Ltd. as the reference fuel for
This is recommended by Engine Combustion Network (ECN) guide-
this study. The properties of n-pentanol, diesel and other short-
lines and adopted in previous studies [55,56]. The threshold stan-
chain alcohols are shown in Table 1. The maximum volume blend-
dard has proved was sufficiently above the noise floor and cool-
ing ratio of n-pentanol has reached 45% by now [22]. Therefore,
flame chemiluminescence recorded by the camera, and sufficiently
this study was focused on three fuels, including D100, D80P20
under the high-temperature chemiluminescence. Once the maxi-
and D60P40 (blending n-pentanol with diesel at blending ratios
mum luminosity intensity inside the region of interest exceed
of 0/100, 20/80 and 40/60 by volume respectively). Solubility of
the ignition standard, it could be recognized as the occurrence of
all these fuels was tested and no phase separation was found after
ignition. The elapsed time between the start of injection and this
48 h.
moment is defined as the ignition delay. The high intensity area
A pre-combustion technique was used to generate the high
is defined as the ignition location. For the second optical arrange-
temperature and high pressure gas in the combustion vessel,
ment, two ND8 dimmer lenses were applied to eliminate the high
which was described in details by Siebers et al. [51] and Huang
temperature chemical luminescence and the light signal captured
et al. [52]. The chamber was filled with C2H2, N2 and O2 in pre-
by the camera was merely the incandescence radiated from the
calculated proportion to form a 15 kg/m3 density mixture. After
high-temperature soot particles [53,57].
spark ignition, temperature and pressure of the mixture would
go up fast and then decrease gradually. When the products of the
pre-combustion cool to a preselected pressure and temperature 3. Results and discussion
state, the controller triggers the injector to start injection and the
high-speed digital CCD camera to record spray flame images simul- 3.1. Ignition characteristics
taneously. In order to ensure a precise control of the charging pres-
sure, components and combustion pressure, an independent As mentioned earlier, the time-sequence of broadband chemilu-
pressure acquisition system was designed. This system is com- minescence images were acquired through the high-speed imaging
posed of a Kistler 6052C pressure sensor, a Kistler 5018 charge technique. These images recorded the high-temperature auto-
amplifier and a NI USB-6251M high-speed data sample card. It ignition processes of tested fuels under various conditions intu-
combines with the other distribution units to create a closed- itively [54]. Typical sequences of broadband chemiluminescence
loop control system. This system also collects pressure information images of three tested fuels are visible in Fig. 3. The example cho-
during the pre-combustion and spray combustion processes. The sen is for the ambient temperature of 800 K and oxygen content of
spray combustion of tested fuels was explored under various ambi- 15% condition. The displayed sequence begins slightly prior to
ent temperatures (800 K, 1000 K and 1200 K) and oxygen concen- chemiluminescence appearance and ends shortly after ignition,
trations (10%, 15% and 21%). Other experimental parameters such and blue lines borders high-temperature reactivity area (pixels
as injection characteristics and ambient density were kept consis- whose intensity is greater than ignition standard) in each image.
tent. The tested conditions of the present study are summarized in We could easily visualize the whole ignition process and
Table 2. acquire the ignition information from those chemiluminescence
The sources of error in this study mainly include the random image sequences. When injection process began, liquid fuel
error caused by spray combustion processes, and systematic error entered into the CVCB with a high velocity. Then liquid fuel broke
introduced during the gas filling process and signal measurement. up, vaporized and mixed with hot air to form richer mixture. After
In order to increase the accuracy of the experimental results, the a certain time of further mixing, richer mixture became more
experiments were repeated five times at each test condition. The homogeneous and started emitting very weak chemiluminescence.
average value of these five tests is repeated in the present paper. This emission is low-temperature, or cool-flame chemilumines-
522 Y. Ma et al. / Applied Energy 185 (2017) 519–530

Fig. 1. Schematic of the constant volume combustion chamber system.

Table 1
Fuel properties of n-pentanol, diesel and other short-chain alcohols [16,49,50].

Items Diesel Methanol Ethanol n-Butanol n-Pentanol

Molecular formula Average C14H30 CH3OH C2H5OH C4H9OH C5H11OH
Molecular weight (kg/kmol) 198.4 32.04 46.07 74.12 88.15
Cetane number 56 5 8 17 20
Oxygen content (wt%) 0 49.93 34.73 21.59 18.15
Stoichiometric air/fuel ratio 14.95 6.46 8.98 11.17 11.74
Density at 20 °C (kg/m3) 831 791.3 789.4 809.7 814.8
Viscosity at 40 °C (mm/s2) 2.72 0.58 1.13 2.22 2.89
Low heating value (MJ/kg) 42.68 19.58 26.83 33.09 35.06
Latent heating at 25 °C (kJ/kg) 270 1162.64 919.6 707.9 647.1
Surface tension at 20 °C (10 3 N/m) 27.5 22.5 22.3 23.7 24.7
Solubility in water (g/L) Immiscible Miscible Miscible 77 22
Blending stability with diesel (>0 °C, v/v) – Unstable <10% All blends All blends
Boiling point (°C) 223 (T10) 64.7 78.3 117.5 138
266 (T50)
311 (T90)
Flash point (°C) >55 11 17 35 49

Table 3
Table 2 Camera properties.
Test conditions.
Broadband High-temperature
Fuel tested D100, D80P20, D60P40 chemiluminescence combustion
Injector type Single-hole, sac type Camera MotionPro Y4-S1
Orifice diameter (mm) 0.234 Lens Tokina 100 mm (f/2.8)
Injection pressure (bar) 1500 Frame rate 20,000 fps
Injection duration (ms) 2.5
Ambient temperature (K) 800, 1000, 1200 Filter 600 nm low pass Two ND8
Ambient oxygen (vol%) 21, 15, 10 Exposure time 46 ls 8 ls
Ambient density (kg/m3) 15 Resolution 1024  280 640  280
Scale 0.135 mm/pixel 0.204 mm/pixel
Ambient oxygen after pre-combustion (vol%) CO2 H2O N2
O2 21 8.17 4.08 66.75
O2 15 8.17 4.08 72.75
O2 10 8.17 4.08 77.75
resulted in strong chemiluminescence (the area bordered in blue1
line in Fig. 2). The transition time from cool-flame chemilumines-
cence to high-temperature chemiluminescence occurs in about

cence, which is released from a series of chemical reactions under

low temperature range [58]. The continuous low temperature reac- 1
For interpretation of color in Figs. 2 and 7, the reader is referred to the web
tion kept releasing heat and accumulating free radicals, finally version of this article.
 Y. Ma et al. / Applied Energy 185 (2017) 519–530 523

Maximum luminosity intensity (a.u.) 103 mixing time and cause high temperature ignition to occur at far-
high-temperature ther downstream. Another important observation is that pentanol
chemiluminescence level blends have a relatively larger cool-flame chemiluminescence area
over the pure diesel. It indicates that pentanol blends tend to ignite
102 ignition threshold more homogeneously. In other words, a larger amount of fuel have
taken part in re-ignition reactions after pentanol is added. This also
cool-flame
contributes to the low reactivity of pentanol, which more likely
chemiluminescence
10 1 shifts the combustion mode to the ‘‘mainly pre-mixed” one.
However, the inhibitory effect on ignition has not yet been
monotonically enhanced as expected while increasing the pentanol
blending ratio to 40%. In Fig. 3, D60P40 performed a higher reactiv-
100 ity compared to D80P20, for the decreased ignition delay and
shortened ignition distance. It can be explained that addition of
0.0 0.5 1.0 1.5 2.0 2.5 3.0 pentanol could effectively enhance air entrainment capacity. We
Time (ms) has found through non-combustion spray images that pentanol
blending fuels have a better air-fuel mixing compared with pure
Fig. 2. The maximum luminosity intensity inside the region of interest as ignition
occurs and combustion progresses (Tamb = 800 K, O2% = 15%, qamb = 15 kg/m3,
diesel. The more mass of hot air the spray entrains in, the more
pinj = 1500 bar and fuel = D80P20). energy and oxygen content the mixture will have. Therefore, from
the aspect of improving physical mixing, blending pentanol into
diesel could accelerate the rate of ignition reaction. According to
0.1 ms, and it is in good agreement with others’ studies [54,58]. Once the above discussion, we should keep in mind that the ignition
high-temperature chemiluminescence exceeded the ignition stan- characteristics are results of interaction between physical mixing
dard, this moment could be regarded as ignition moment, and igni- and chemical activity. Although its cetane number is lower than
tion times was calculated by past image counts while ignition D80P20, D60P40 has a more significant improvement on air
location directly measured from the image of this moment. entrainment capacity, which is the reason why D60P40 showed a
As can be seen in Fig. 3, addition of pentanol into diesel has a higher reactivity in this condition. The next part will introduce
distinct inhibitory effect on ignition in the specific condition. In ignition information of more comprehensive conditions to further
details, comparing to pure diesel, pentanol blends obviously pro- clarify the blending effect on ignition characteristics.
long the ignition delay and lengthen the ignition distance. This is A series of experiments were carried out using pure diesel D100
mainly due to pentanol’ low cetane number and high latent heat and pentanol blends D80P20, D60P40 at ambient temperature of
of evaporation. These factors significantly suppress the occurrence 800–1200 K, with ambient oxygen content ranging from 10% to
of spray ignition. A longer ignition delay provide fuels with more 21%. Fig. 4 shows the quantitative comparison of the ignition time

Time (ASOI) D100 D80P20 D60P40

0.60ms

0.70ms

0.80ms

0.90ms

1.00ms

1.10ms

1.20ms

Fig. 3. Broadband chemiluminescence images for diesel and n-pentanol blends under the ambient temperature of 800 K and oxygen concentrations of 15% condition. High-
temperature reactivity borders are shown in blue line. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
524 Y. Ma et al. / Applied Energy 185 (2017) 519–530

phase. Under an oxygen-lean surrounding, lack of oxygen is the

(a) 10% O2 main factor limiting the process of pre-ignition reactions. Pen-
2.4
Ignition time (ms)

tanol’s mixing-improved ability make the ignition-promoted effect

1.8 D100 occupy the dominant position. Once surrounding becoming
D80P20
oxygen-rich, the importance of air entrainment turns deflated,
1.2 D60P40
and adding pentanol performs rather more inhibitory effect.
The ignition distance for diesel and pentanol blends at various
0.6
ambient temperatures and oxygen concentrations is shown as
0.0 Fig. 5. Generally, addition of pentanol would significantly increase
the ignition distance under all test conditions except D60P40,
1.0 (b) 15% O2
which possesses a greater blend proportion of pentanol but exhi-
Ignition time (ms)

0.8 bits shorter ignition distances than D80P20 in low temperature

and low oxygen contents environment. While under the condition
0.6 of 21% O2, the ignition distance increases monotonously with the
0.4 pentanol blend proportion. The results show an accordant trend
with ignition times as illustrated in Fig. 4, and indicate the complex
0.2
impact of blending pentanol on spray ignition process from the
0.0 spatial aspect. In short, the chemical inhibitory effect of blending
0.5 (c) 21% O2 pentanol has gradually become the dominated factor in spray igni-
Ignition time (ms)

tion process when the oxygen content of the surrounding is getting

0.4 richer. Overall, the longer ignition delay time or distance could
0.3 provide more mixing/transport time or space, and pentanol has a
relatively lower stoichiometric equivalence ratio; the above two
0.2 reasons lead to a great reduction of the local equivalence ratio at
0.1 the ignition position and they could be beneficial to clean combus-
tion in diesel engines.
0.0
800 900 1000 1100 1200 3.2. Combustion characteristics
Temperature (K)
3.2.1. Combustion pressure and heat release rate
Fig. 4. Ignition time for diesel and n-pentanol blends at various ambient temper- Fig. 6 illustrates the combustion pressure and apparent heat
atures and oxygen concentrations.
release rate (AHRR) for pentanol-diesel blend fuels and pure diesel
under four representative conditions. The combustion pressure is
of the tested fuels under the extensive experimental conditions. the total pressure derived from the transducer minus the initial
From the first glimpse at the result, we could easily find that rais- ambient pressure at the time of injection. The error bars of D100
ing ambient temperature and increasing oxygen content both are given to represent the similar standard deviation of all test
markedly shorten the ignition delay of both pure diesel and pen- fuels (the same as following figures). In order to confirm the rela-
tanol blends. The liquid fuels would more easily evaporate under tionship of the cycle energy and the spray combustion characteris-
a higher temperature environment. It helped to promote air-fuel tics, we firstly measured the cycle injected mass of all blends by an
mixing quality and form mixture with higher heat density, which electronic balance; then determined the cycle energy by a term of
would advances ignition. Meanwhile, an oxygen-rich environment the cycle injected mass times the low heating value of each fuel;
will speed up the reduction of the equivalence ratio in the spray finally, the cycle input energy of D100, D80P20 and D60P40 were
region and make it easier to reach flammability limit. This result calculated to be 1541.6 J, 1517.7 J and 1495.1 J, respectively. Obvi-
is consistent with previous experiment and modeling conclusions ously, the cycle energy of fuel exhibited a downtrend with the pen-
[1,59–61]. tanol blend ratio increased. Reducing input energy is certain to
Fig. 4 also shows D100 has shorter ignition delays than both decrease the total heat release and further lower the maximum
pentanol blends under all ambient temperature and oxygen con- combustion pressures. This is totally in consistent with the
centration conditions due to its extra high cetane number. An observed results, which the maximum combustion pressures of
interesting behavior was found that the addition of pentanol into pentanol blends are slightly lower than the pure diesel in Fig. 6.
diesel has a complex impact on spray ignition process, which These results also reflect two obviously different effects of pen-
mainly related to pentanol blend portion and ambient oxygen con- tanol additives on the heat release rate of spray combustion in low
centration. Compared to D100, a moderate pentanol blend portion and high ambient oxygen concentration. At a low ambient oxygen
of 20% in volume ratio prolonged ignition delay time under various concentration of 10% (Fig. 6a and c), the heat release rate peak of
ambient temperature and oxygen concentration. However, when pentanol/diesel blends was lower than that of neat diesel, and
increasing the pentanol blend portion ratio to 40%, spray ignition the combustion phase of diesel was also obvious retarded while
time became more sensitive to oxygen concentration. Under the blending with pentanol. However, for a normal ambient oxygen
oxygen concentration of 10% and 15%, D60P40 ignited ahead of concentration of 21% (Fig. 6b and d), the peak of heat release rate
D80P20 at all temperature conditions. However, the ignition time slightly increased and the combustion phase also advanced after
of D60P40 fell behind the other fuels in higher ambient oxygen blending with pentanol. The above opposite effects are mainly
concentration of 21%, especially under the conditions of ambient because of the highly dependence of pentanol oxidization on oxy-
temperature below 1000 K. It can be explained that blending pen- gen under low and intermediate temperatures regime [62]. Under
tanol brings a complicated effect on spray ignition process. On the that condition, a large amount of oxygen has been consumed by
one hand, the low cetane number of pentanol would pose a the formation of aldehydes, which is via the reaction of the alpha
restraining effect on ignition; on the other hand, pentanol’s high fuel radical with oxygen; this aggravates the shortage of oxygen
volatility and low surface tension could help to entrain in more while under the oxygen-lean condition, and further hinders the
fresh air, which will provide more oxygen and advance ignition formation of QOOH which is greatly depended on the ambient oxy-
 Y. Ma et al. / Applied Energy 185 (2017) 519–530 525

120 volume cycle, which has the highest efficiency. Therefore, we

Ignition distance (mm) Ignition distance (mm) Ignition distance (mm)
(a) 10% O2 believe the rapid combustion characteristics of pentanol blends
90 make them have the ability to improve the thermal efficiency of
D100 real engines.
D80P20
60
D60P40 3.2.2. Natural flame luminosity
Spectroscopic studies of hydrocarbon flames [63,64] found the
30
natural luminosity in the combustion of fuels mainly included
intermediate specie radicals chemiluminescence and soot incan-
500
descence, and the chemiluminescence of the jet is soon hidden
(b) 15% O2 by this early soot radiation that is about three orders of magnitude
40
brighter after ignition [65]. In order to avoid over-saturation on the
30 CMOS camera images, this study used two ND8 filters to reduce the
natural luminosity and the brightness of flames were decreased to
20 1/64 of its original value. As a result, chemiluminescence of radi-
cals is filtered almost completely, and the natural luminosity is
10
dominated by soot particles radiation in spray combustion condi-
300 tions [64]. This convenient optical method has been widely used
(c) 21% O2 in spray combustion studies of novel and alternative liquid fuels
24 recently [52,53].

18
3.2.2.1. Flame evolution. Fig. 7 shows a typical natural flame time
12 evolution of D60P40 at ambient temperature of 800 K and oxygen
concentration of 21%. The snapshots of each time step has been
6 pseudocolor processed for a better display effect. The color bar at
the bottom only represents arbitrary unit scale consistent over
0 the whole combustion process. The green vertical line is the instant
800 900 1000 1100 1200 spray tip penetration under same condition but with oxygen con-
Temperature (K) centration of 0% to prevent ignition happening. We can find that
stronger luminosity appeared at about 0.75 ms ASOI, which was
Fig. 5. Ignition distance for diesel and n-pentanol blends at various ambient
slightly lagged behind ignition time (about 0.45 ms ASOI from
temperatures and oxygen concentrations.
Fig. 3). The luminosity was firstly located in the downstream half
of spray, where belonged to fuel-rich region. It is consistent with
the soot formation rule of mixing-controlled combustion concep-
gen content [35]. As a necessity for chain-branching reaction, the tual model raised by Dec [39]. Then the strong flame luminosity
lack of QOOH leads to the retardation of combustion process. In region continuously moved downwards with axial momentum
the view of application in a real engine, the comparison of heat provided by high pressure injection system, and soon exceeded
release rate for diesel and pentanol blends illustrates pentanol the non-reaction spray penetration. In this period, the penetration
blends performs a shorter combustion duration in most conditions ratio of reaction spray to non-reaction spray starts increasing with
when compared with pure diesel. This means more fuel will be time. This is called as ‘‘Acceleration phase” by Payri et al. [66], and
consumed for outputting torque within a certain period in a real Huang et al. [52] suggests that it is mainly attributed to the ther-
engine fueled with pentanol blends. In those conditions, the ther- mal expansion of burning gases. Besides, flame structure has grad-
modynamic cycle in the engine is more close to the constant- ually transferred from a homogeneously bright spot developed into

1.5 400
(a) 800K, 10%O2
1.2 320
Pressure (bar)

AHRR (kJ/s)

(b) 800K, 21%O 2

0.9 240
0.6 160
0.3 80
0.0 0
1.5 400
(c) 1200K, 10%O 2 (d) 1200K, 21%O 2
1.2 320
Pressure (bar)

AHRR (kJ/s)

0.9 240
D100
0.6 D80P20 160
D60P40
0.3 80
0.0 0

0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0
Time (ms) Time (ms)
Fig. 6. Combustion pressure and heat release rate for diesel and n-pentanol blends at various ambient temperatures and oxygen concentrations.
526 Y. Ma et al. / Applied Energy 185 (2017) 519–530

Fig. 7. Natural flame evolution for D60P40 at ambient temperature of 800 K and oxygen concentration of 21%.

inhomogeneous spots with obvious brightness gradients. It implied FLoL has always been considered to be controlled by ignition delay,
that the spray flame turned from premixed flame to diffusion and usually a longer ignition delay results in a longer steady FLoL
flame, and the transition time is at about 1.25 ms ASOI. [68]. Our results are generally in good agreement with this conclu-
The diffusion flame impinged on the wall at around 1.75 ms and sion and others experimental results [71,72]; the steady FLoL
spread out along the periphery of the wall. From this moment, the decreases with increasing ambient gas temperature or oxygen con-
flame structure got into a ‘‘quasi steady” status until the end of tent, which could effectively shorten ignition delays and it has
injection. During this period, the nearest distance between injec- been discussed in Section 3.1.
tion hole and spray flame keeps a certain value, which is the named Previous work has reported a significant prolonged effect on the
flame lift-off length (FLoL). The FLoL is considered as the stabiliza- steady FLoL when blending short-chain alcohol with diesel under
tion between of spray turbulent velocity and flame front speed widely conditions [48], and attributed it to the descend of chemical
occurs [45,67]. It is also an important indicator of the mixing status reactivity after addition of short-chain alcohol. However, the cur-
between fuel and air before reaching the combustion region [68], rent work found it was not always consistent with the trends when
which will be discussed in the next section. high alcohol was used. Under the low ambient temperature of
After the end of injection, the major luminosity location passed 800 K, the chemical property such as cetane number and reaction
to the downstream region and even the near-wall region. The rate seems to dominate the length of FLoL; the length of FLoL
upstream flame luminosity became dimmer due to the decreasing was becoming longer with the increasing of pentanol blend ratio.
of local equivalence ratio that promotes the oxidation of soot. Then When ambient temperature was increased to 1000 K, an opposite
the luminosity region gradually narrowed and finally contract to trend had been observed; the steady FLoL of pentanol blends got
the near-wall region. The near-wall luminosity has almost lasted shorter than that of pure diesel and even appeared earlier at low
until 4 ms ASOI. It indicates that soot has a longer existence time oxygen concentration of 10%. As the discussion in Section 3.1 and
in the near-wall region, and this has been confirmed by other opti- Heufer’s work [35], the chemical reactivity of pentanol was
cal methods [47,69]. The reason is the relatively slower oxidation increased rapidly at high temperatures below 1000 K and even
rate of soot, which resulted from poor air entrainment and cooling exceeded its equivalent alkane, while the mixing-improved effect
effect by wall heat transfer. Therefore, reducing near-wall combus- of addition of pentanol still remained at the same level. In other
tion could be beneficial to reduction of soot exhaust emission and words, it meant physical mixing process begins to control the
soot deposition which would damage engine components [70]. length of FLoL. Once ambient temperature reaches 1200 K, the
gap of FLoL caused by different fuels became indistinguishable
3.2.2.2. Flame lift-off length. The transient FLoL for the pure diesel due to the less difference of both chemical and physical delay
and pentanol blends under different ambient temperature and under high temperature environment. Therefore, due to the higher
oxygen content can be seen in Fig. 8. The determination of the FLoL reactivity of high alcohol, the chemical gap between alcohol blends
is based on the flame natural luminosity and the definition has and pure diesel is decreasing, and the physical mixing process is
been described in the previous section. It is necessary to point becoming a more important effect on the steady FLoL. Besides,
out that the natural flame luminosity of pentanol blend fuels in the control mechanism of FLoL is more sensitive to ambient tem-
800 K and 10% was barely detectable after using two ND filters, perature rather than oxygen concentration.
which means little soot particles has formed in the condition. This
is consistent with the investigation result of a DI diesel engine 3.2.2.3. Luminosity intensity analysis. Fig. 9 presents the spatially
fueled with pentanol/diesel blends up to a high EGR range [29]. integrated natural luminosity (SINL) for pure diesel and pentanol
Therefore, the FLoL of pentanol blends under 800 K and 10% O2 blends under different ambient oxygen content and SINL is calcu-
ambient environment is not included in this study. lated by summing up the values of all pixels in each image. As
Fig. 8 shows that these FLoLs soon got into quasi-steady status mentioned at the beginning of Section 3.2.2, the natural luminosity
after their appearance, which were named steady FLoL. The steady is dominated by soot particles radiation in spray combustion con-
 Y. Ma et al. / Applied Energy 185 (2017) 519–530 527

120

Lift-off length (mm)

(a) 800K, 10%O2 (b) 800K, 15%O2 (c) 800K, 21%O2
100
D100
80
D80P20
60 D60P40
40
20
0
Lift-off length (mm)

(d) 1000K, 10%O2 (e) 1000K, 15%O2 (f) 1000K, 21%O2

100
80
60
40
20
0
Lift-off length (mm)

(g) 1200K, 10%O2 (h) 1200K, 15%O2 (i) 1200K, 21%O2

100
80
60
40
20
0
0.0 1.0 2.0 3.0 4.0 0.0 1.0 2.0 3.0 4.0 0.0 1.0 2.0 3.0 4.0 5.0
Time (ms) Time (ms) Time (ms)
Fig. 8. Flame lift-off length for diesel and pentanol blends at various ambient temperatures and oxygen concentrations.

14.0 (a) 800K, 10%O 2 (b) 800K, 15%O 2 (c) 800K, 21%O 2
SINL (a.u.)

10.5 D100
D80P20
7.0 D60P40

3.5

0.0
14.0 (d) 1000K, 10%O 2 (e) 1000K, 15%O 2 (f) 1000K, 21%O2
SINL (a.u.)

10.5

7.0

3.5

0.0
14.0 (g) 1200K, 10%O 2 (h) 1200K, 15%O 2 (i) 1200K, 21%O 2
SINL (a.u.)

10.5

7.0

3.5

0.0
0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0
Time (ms) Time (ms) Time (ms)
Fig. 9. Spatially integrated natural luminosity (SINL) for diesel and n-pentanol blends at various ambient temperatures and oxygen concentrations.

dition. Hence, SINL can be regarded as an indicator of the formation tion. The higher temperature and oxygen concentration surround-
and oxidization processes of soot to some degree. ing leads to a shorter ignition delay. The combustion phase is
Generally, SINL has a higher peak value in the condition of dominated by spray diffusion at high temperature, which tends
higher ambient temperature and oxygen concentration, which to form a large amount of soot within a short time. From the aspect
means a large formation rate of soot at the early stage of combus- of air mixing, increasing ambient temperature and oxygen concen-
528 Y. Ma et al. / Applied Energy 185 (2017) 519–530

tration also results in a short FLoL; a short FLoL means a limited 100
air-fuel mixing quality before combustion that would promote (a) 800K D100
the formation of soot [73]. Another important trend is that SINL 80
D80P20

TINL (a.u.)
looks narrower under oxygen-rich conditions. It can be explained D60P40
60
that the oxygen-rich environment helps to lower the equivalence
ratio of the burned region and would accelerate soot oxidization 40
in the intermediate and later stages of combustion. Therefore, it
hints comprehensive consideration for controlling appropriate 20
ambient temperature and oxygen content at a specific condition
to lower soot emission. 1000
Other studies have reported a significant inhibition effect on (b) 1000K
flame luminosity by blending short-chain alcohols with diesel 80

TINL (a.u.)
under extensive conditions [47,48,69]. However, as shown in
60
Fig. 8, addition of pentanol into diesel seems to suppress the flame
luminosity slightly and even presents a raising effect under some 40
special conditions. Pentanol blends effectively decreased SINL
under low temperature of 800 K, but increased SINL under inter- 20
mediate temperature of 1000 K. This is consistent with the influ-
ence trend of blending pentanol on the FLoL. It is noteworthy 1000
(c) 1200K
that in high ambient temperature of 1200 K, pentanol blends
80

TINL (a.u.)
slightly lowered SINL with the same FLoL compared with pure die-
sel. This can be explained by two reasons. On the one hand, the 60
overall equivalence ratio of blend fuels has been reduced with
addition of oxygenated fuel pentanol. Pentanol blends would burn- 40
ing at a lower equivalent ratio condition when entraining in basic
same quality of air compared to D100. On the other hand, addition 20
of pentanol leads to the dilution effect, which replaces highly soot-
0
ing components (higher carbon number n-alkanes, aromatics) with
Oxy 10% Oxy 15% Oxy 21%
a relatively smaller carbon number alcohols, and could help to Oxygen concentration
decrease soot concentration to a certain extent [74]. In addition,
the plateau of SINL for pentanol blends were much narrower than Fig. 10. Time integrated natural luminosity (TINL) for diesel and n-pentanol blends
that of neat diesel. This is mainly because the soot oxidation rate at various ambient temperatures and oxygen concentrations.
increases with the increasing of additive pentanol. As the oxygen
contained in pentanol blends; more fuel-borne oxygen will aggres- Under high temperature region, the ignition delay and FLoL gap
sively accelerate soot oxidation during combustion. On the whole, between pentanol blends and pure diesel became negligible; it
although high reactivity of pentanol limits its lengthening effect on means all fuels have a similar air mixing quality before combustion
the FLoL, its low equivalent ratio still helps to decrease soot forma- begins, but pentanol’s low stoichiometric equivalence ratio and the
tion in diesel spray combustion, especially under high temperature dilute effect result in a less soot formation of pentanol blends.
conditions; and the acceleration effect on soot oxidization also
indicates applying pentanol blends can decrease final soot emis- 4. Conclusions
sions from internal combustion engines.
In order to better quantify the natural luminosity characteristics The ignition and combustion characteristics of pentanol/diesel
of the entire combustion duration, we used time integrated natural blends with different blending ratio were investigated in a con-
luminosity (TINL) to be an indication of the soot formation level stant volume combustion chamber. A wide range of experimental
over the entire combustion cycle. As has been described in Refs. conditions were adopted, including the ambient temperatures
[48,75], TINL was calculated by integrating SINL with time. ranging from 800 K to 1200 K and oxygen concentrations ranging
Fig. 10 illustrates TINL for diesel and pentanol blends at various from 10% to 21%. Following observations are made from the results
ambient temperatures and oxygen concentrations. The result also obtained:
show a complex effect of addition of pentanol on TINL, and this
effect is more sensitive to ambient temperature. Under ambient (1) Pentanol blends show longer ignition delay and ignition dis-
temperature of 800 K and 1200 K, TINL gradually decreased with tance than pure diesel under all experimental conditions.
the pentanol blend ratio increased, while the influence tendency The effect of pentanol ratio in blends on ignition character-
seems to be insignificant under ambient temperature of 1000 K. istics is more sensitive to the oxygen concentration; under
Combining with the discussion in the above section and pentanol’s low oxygen concentration condition of 10% and 15%,
oxidation kinetic modeling [37], the result reflects the different D60P40 exhibits shorter ignition delay and ignition distance
influence mechanisms of blending pentanol on soot formation in than those of D80P20; but the ignition delay and ignition
diesel spray combustion: (a) the low chemical reactivity of pen- distance increase monotonously with the pentanol ratio
tanol dominated the length of FLoL under low temperature region. increases under high oxygen concentration condition of
The more pentanol blended in, the longer FLoL was and the less 21%. Generally, increasing ambient temperature and oxygen
soot formed. (b) When ambient temperature increased to interme- concentration both could reduce the ignition gap between
diate temperature region, pentanol’s chemical reactivity enhanced each fuel significantly.
rapidly and the physical mixing process further exerted more (2) Addition of pentanol shows an obviously inhibiting effect on
important role in ignition. Due to the better mixing quality before heat release process under oxygen-lean atmosphere. The
combustion, pentanol blends had shorter ignition delay and blending effect turns into the opposite side, which raising
shorter FLoL. Hence, it resulted in a more diffusive dominated com- the heat release peak and advancing combustion phase,
bustion and roughly equal soot formation compared to D100. (c) while under oxygen-rich atmosphere.
 Y. Ma et al. / Applied Energy 185 (2017) 519–530 529

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