Energy Conversion and Management 119 (2016) 246–256

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

A comparative analysis on combustion and emissions of some next

generation higher-alcohol/diesel blends in a direct-injection diesel
engine
B. Rajesh Kumar a,b,⇑, S. Saravanan c, D. Rana d, A. Nagendran e
a
Research Centre, Department of Mechanical Engineering, Sri Venkateswara College of Engineering, Chennai, TN, India
b
IC Engines Division, Department of Mechanical Engineering, Jeppiaar Institute of Technology, Chennai, TN, India
c
Engine Research Lab, Department of Mechanical Engineering, Sri Venkateswara College of Engineering, Chennai, TN, India
d
Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
e
PG & Research Department of Chemistry, Polymeric Materials Research Lab, Alagappa Govt. Arts College, Karaikudi, TN, India

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

Article history: Higher alcohols are attractive next generation biofuels that can be extracted from sugary, starchy and
Received 18 February 2016 ligno-cellulosic biomass feedstocks using sustainable pathways. Their viability for use in diesel engines
Received in revised form 14 April 2016 has greatly improved ever since extended bio-synthetic pathways have achieved substantial yields
Accepted 15 April 2016
of these alcohols using engineered micro-organisms. This study sets out to compare and analyze the
Available online 20 April 2016
effects of some higher alcohol/diesel blends on combustion and emission characteristics of a direct-
injection diesel engine. Four test fuels containing 30% by vol. of iso-butanol, n-pentanol, n-hexanol and
Keywords:
n-octanol (designated as ISB30, PEN30, HEX30 and OCT30 respectively) in ultra-low sulfur diesel
Diesel engine
Combustion analysis
(ULSD) were used. Results indicated that ISB30 experienced longest ignition delay and produced
Pentanol highest peaks of pressure and heat release rates (HRR) compared to other higher-alcohol blends.
Long-chain alcohol The ignition delay, peak pressure and peak HRR are found to be in the order of (from highest to lowest):
Butanol ISB30 > PEN30 > HEX30 > OCT30 > ULSD. The combustion duration (CD) for all test fuels is in the
Higher carbon alcohol sequence (from shortest to longest): ISB30 < PEN30 < HEX30 < OCT30 < ULSD. Experimental mass fraction
burned profiles fitted using the Wiebe’s function revealed that the burning rate at the start of combustion
is rapid for ISB30 followed by PEN30, HEX30, OCT30 and ULSD. From the emissions standpoint, NOx
emissions decreased for all blends at low/medium loads but increased for PEN30 and HEX30 at high
engine loads only. Smoke opacity is low for all blends due to their oxygenated nature and was of the order
(from highest to lowest): ULSD > OCT30 > HEX30 > PEN30 > ISB30. HC emissions are high for ISB30 and
PEN30 while it decreased favorably for HEX30 and OCT30. It was of the order (from highest to lowest):
ISB30 > PEN30 > ULSD > HEX30 > OCT30. CO emissions of the blends followed the trend of smoke
emissions and remained lower than ULSD with the following order (from highest to lowest):
ULSD > OCT30 > HEX30 > PEN30 > ISB30.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction (green-house gases) emissions, toxic pollutants (smoke and NOx)

Diesel engines are more popular energy conversion devices
because of their higher fuel conversion efficiency, higher torque
capability, higher durability and lower hydrocarbon and carbon
monoxide (HC & CO) emissions when compared to gasoline
engines. Increasing concerns of fossil fuel depletion, oil-price
volatility, burgeoning energy demands, global warming by GHG
⇑ Corresponding author at: IC Engines division, Department of Mechanical
Engineering, Jeppiaar Institute of Technology, Chennai, TN, India.
E-mail addresses: rajesh_thermal@yahoo.com (B. Rajesh Kumar), saran@svce.ac.
in (S. Saravanan), rana@uottawa.ca (D. Rana), nagimmm@yahoo.com (A. Nagendran).
and rigorous emission regulations are driving the scientific com-
munity to find alternative renewable biofuels for use in diesel
engines. Recently higher alcohols have gathered interest among
engine researchers to use them in diesel engines either as a neat
fuel or as a blending component because they offer higher calorific
value, higher cetane number, better blend stability and lower
vapor pressure when compared to other widely-studied lower
alcohols like ethanol and methanol. The term ‘higher alcohol’ refers
to a series of straight and branched chain alcohols that consists of
four or more carbon atoms like butanol (C4), pentanol (C5), hexanol
(C6), heptanol (C7), octanol (C8), dodecanol (C12) and phytol (C20)

http://dx.doi.org/10.1016/j.enconman.2016.04.053
0196-8904/Ó 2016 Elsevier Ltd. All rights reserved.
 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256 247

Fig. 1. Molecular structure of some higher alcohols.

Table 1
Properties of higher alcohols [1,5] in comparison with diesel and other lower alcohols.

Properties Diesel Methanol Ethanol Iso-Butanol n-Pentanol n-Hexanol n-Octanol

Molecular weight (kg/kmol) 190–211.7 32.04 46.07 74.12 88.15 102.18 130.23
C (wt%) 86.13 37.48 52.14 64.82 68.13 70.52 73.72
H (wt%) 13.87 12.48 13.02 13.49 13.61 13.70 13.82
O (wt%) 0 49.93 34.73 21.59 18.15 15.70 12.29
Stoichiometric A/F ratio 14.67 6.47 9.01 11.21 11.76 12.15 12.71
Solubility (g/L) Immiscible Miscible Miscible 77 22 7.9 4.6
Cetane number 52 5 8 <15 20 23 37
Self-ignition temperature (°C) 254–300 463 420 415 300 285 270
Density (kg/m3) at 15 °C 835 791.3 789.4 802 814.8 821.8 827
Viscosity at 40 °C (mm/s2) 2.72 0.58 1.13 2.63 2.89 4.64 5.8
Lower heating value (MJ/kg) 42.49 19.58 26.83 33.64 34.65 36.4 37.53
Latent heat of evaporation (kJ/kg)a 270–375 1162.64 918.42 684 647.1 603.0 545.0
Vapor pressure (mmHg) 0.4 127 55 10.4 6 0.928 0.08
Boiling point (°C) 180–360 64.7 78.3 108 137.9 157 195
Flash point (°C) >55 11–12 17 28 49 63 81
a
Data from Refs. [6,7].

Table 2
Microbial production of higher alcohols from engineered microbes with their yield.

Higher alcohol Engineered host organisms Source Yield

Iso-butanol E. coli Glucose 22 g/L [9]
E. coli Glucose 50 g/L [12]
Saccharomyces cerevisiae Glucose 0.143 g/L [13]
Clostridium cellulolyticum Cellulose 0.66 g/L [14]
Ralstonia eutropha Formate 0.846 g/L [15]
Corynebacterium glutamicum Glucose 12.6 g/L [16]
Synechococcus elongates CO2 + H2O + Light 0.45 g/L [17]
Bascillus subtilis Glucose 2.62 g/L [18]
n-pentanol E. coli Glucose 204.7 mg/L [11]
E. coli Glucose 2.22 g/L [19]
n-hexanol E. coli Glucose 302 mg/L [10]
E. coli Glucose 18.5 mg/L [11]
E. coli Glucose 47 mg/L [19]
Clostridium carboxidivorans Syngas 0.9 g/L [20]
Clostridium acetobutylicum Glucose 30 mg/L [21]
Ralstonia eutropha Glucose 280 mg/L [21]
n-octanol E. coli Glucose 62 mg/L [5]
E. coli Glucose 2 mg/L [10]
E. coli Glucose 70 mg/L [21]

[1]. The molecular structures of some higher alcohols are portrayed
in Fig. 1.
Higher alcohols are found to be less corrosive on fuel injection
and delivery systems due to their less hygroscopic nature than
ethanol [2]. They have high flashpoints that offer safer storage
and handling within the existing fuel distribution infrastructure.
Their lower vapor pressures cause less evaporative emissions [3].
Though longer-chain alcohols have less oxygen content, they can
still enhance the premixed combustion phase with their relatively
longer ignition delays allowing sufficient mixing of air/fuel and
also improve the diffusion combustion phase [1]. Furthermore,
alcohols with longer carbon chains consume less energy during
its production when compared to other lower alcohols since the
biological process of breaking down large macromolecules can stop
earlier [4]. The properties of higher alcohols in comparison with
diesel and other lower alcohols are listed in Table 1.
The use of higher alcohols was earlier thwarted by high produc-
tion costs, prolific use in food industry and limited production from
non-petroleum resources [8]. Higher alcohols have never been able
to be produced in larger quantities that make them potentially
viable for use in diesel or gasoline engines until Atsumi et al. [9]
achieved a high yield of 20 g/L of iso-butanol from glucose using
the valine pathway in a lab-scale fermentor employing engineered
Escherichia coli. Since then, bio-synthetic pathways have been
extended to produce n-pentanol, n-hexanol, n-heptanol and
n-octanol by employing larger substrates [10,11]. Table 2 provides
the details of microbial production of these alcohols from
engineered micro-organisms with their yield data.
It could be inferred from Table 2 that the last decade has wit-
nessed a significant amount of research to produce greater yields
of higher alcohols through biosynthesis. To complement these
efforts, several experimental and chemical kinetic modeling stud-
ies have been carried out. Fundamental combustion studies on
iso-butanol [22–27], n-pentanol [28–32], n-hexanol [30,33,34]
and n-octanol [6,35] were conducted which included information
on its oxidation, laminar burning velocities, flame structure,
248 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256
reaction rates and pathways, species concentration data, stable
intermediate species and ignition delay times.
The compatibility of these alcohols in diesel engines has
prompted engine researchers to use them in their neat or blended
form in diesel engines to analyze their combustion, performance
and emission characteristics under various combustion strategies.
Unlike n-butanol, which is heavily researched in the last 5 years,
only a handful of research exists with iso-butanol [8,36–41] and
n-pentanol usage [4,41–46] in diesel engines. These studies collec-
tively demonstrated that ignition delay increased with increasing
alcohol content in the blends as a result of their lower cetane num-
ber. The peaks of in-cylinder pressure and heat release rate
increased with alcohol addition as a result of enhanced premixed
combustion phase caused by the prolonged ignition delay. Smoke
emissions generally decreased with increasing alcohol content in
the blends. NOx emissions remained low with iso-butanol/diesel
blends at all loads and n-pentanol/diesel blends only at low/med-
ium loads. NOx emissions increased invariably at high loads with
the addition of n-pentanol.
So far only one study has investigated the combustion, emission
and performance of a diesel engine using n-hexanol/diesel blends
up to 50% by vol [47]. Addition of n-hexanol also increased the
ignition delay along with slightly higher peaks of pressure and
HRR. NOx increased but the smoke was substantially reduced with
n-hexanol addition. Till date, there have been far fewer studies that
used n-octanol in considerable proportions in diesel engines.
McCormick et al. [48] reported simultaneous reduction of PM
and NOx by 12% and 3%, respectively, by adding 1-octanol at
2 wt% of oxygen with diesel in a 2-stroke diesel DI engine. Heuser
et al. [49] used neat n-octanol in a compression-ignition engine
and reported PM emissions to reduce by 20-fold than a diesel
fuelled engine. Zhang et al. [50] tested n-octanol/diesel blend
(30 vol%) with hydro-treated vegetable oil (HVO) or di-tertiary-
butyl peroxide (DTBP) as cetane improvers at various operating
points from the European stationary cycle and obtained less smoke
and high NOx. Deep et al. [51] compared the use of 1-octanol at dif-
ferent blend ratios (10%, 20% and 30% v/v) with diesel in a medium
capacity unmodified diesel engine. NOx levels were reduced with
increasing octanol content in the blend and the engine efficiency
was slightly affected. Heuser et al. [6] analyzed the combustion
and emission behavior of 1-octanol and di-n-butyl ether in a single
cylinder engine. Ignition delay prolonged with 1-octanol. Soot
emissions reduced by 5-fold and a reduction in total particle num-
ber by up to 80% was achieved. Hoppe et al. [52] found favorable
soot/NOx trade-off over the entire engine load range with n-
octanol/diesel blends. For further reading on higher alcohols usage
in diesel engines, a detailed and exhaustive review can be obtained
from a recent article by this research group [1].
Filling a gap in the existing body of literature of higher alcohols,
this research presents a vis-a-vis study that compares and analyzes
four higher alcohol/diesel blends (iso-butanol, n-pentanol,
n-hexanol and n-octanol) in the same light-duty, single cylinder,
and direct injection diesel engine under similar operating condi-
tions. To the authors’ knowledge, this is the first time that such a
comparative evaluation is reported for many higher alcohol/diesel
blends in the same engine and operating conditions concerning
combustion and emission characteristics of the engine.
2. Materials and methods
2.1. Test fuels
Iso-butanol (Purity: 99%, CAS No: 78-83-1) and n-pentanol
(Purity: 98%, CAS No: 71-41-0) were procured from AVRA Synthe-
sis, India. n-hexanol (Purity: 98%, CAS No: 108-93-0) and n-octanol
(Purity: 99%, CAS No: 111-87-5) were procured from Merck Millipore,
India. All these alcohols are certified to be of analytical grade.
Ultra-low sulfur diesel (ULSD) fuel which forms the reference fuel
for this study was obtained from Indian oil corporation, Chennai.
The test fuels were prepared by mixing all alcohols individually
with ULSD in blending ratio of 30/70 by vol. and are designated
as ISB30, PEN30, HEX30 and OCT30. No cetane improvers or surfac-
tants were added. The choice of 30% higher alcohol/diesel blend is
governed by the fact that the variations of combustion and emis-
sion parameters are relatively discernible for higher percentages
of these alcohols. The choice of iso-butanol over n-butanol in this
study was made after carefully considering several advantages of
iso-butanol over n-butanol. In the recent years, iso-butanol is
increasingly favored by the industry because n-butanol production
technology is handicapped by high energy cost due to its
production in low concentrations and significant volumes of water
processed even with new Clostridia strains [27]. E. coli can be
engineered to produce 22 g/L of iso-butanol, a value that exceeded
most of the native n-butanol production quantities using the
valine biosynthetic pathway [53,54]. Moreover, optimization of
iso-butanol production from glucose has achieved a yield of 50 g/L
using the valine pathway [13] when compared to the modified
CoA (Coenzyme A) pathway that yielded only 30 g/L of n-butanol
[55] in lab-scale fermenters with engineered E. coli. Another advan-
tage is that existing ethanol plants that use corn, sugarcane and
cellulose as feedstock can be re-purposed to produce iso-butanol
by just modifying the bio-catalyst as demonstrated by Gevo [56].
Further, iso-butanol/diesel blends reportedly present higher peak
pressures and higher premixed heat release rates than n-butanol/
diesel blends [39]. It also causes a longer ignition delay than
n-butanol/diesel blends which is necessary for effective premixing
of air/fuel mixture before combustion and iso-butanol produces
lowest smoke emissions among all the other isomers [57,58].
The properties of test fuels were measured by ASTM test meth-
ods at the Polymeric Materials Research Laboratory in Alagappa
College, Tamil Nadu and are presented in Table 3. The cetane
indices of the test fuels were estimated by the four variable equa-
tion as stipulated by ASTM 4737 using the test fuel’s density and
T10, T50 and T90 distillation points. Diesel injected at standard
injection timing is designated as ‘ULSD’ throughout the discus-
sions. Solubility of all blends was checked and no phase separation
was found after several weeks of observation. However the blends
were stirred well just before refueling using an electric mixer to
ensure consistency.
Fig. 2 illustrates the variations of ASTM properties for all higher
alcohol/diesel blends. Since these properties are of different units,
they are scaled downed to dimensionless numbers in order to
represent them in a single graph. Equally from Table 1 and Fig. 2,
the cetane number is seen to be increasing from iso-butanol to
n-octanol both in its neat and blended states. The fuel molecular
structure affects the combustion process mainly through ignition
delay, which is a direct result of low temperature ignition reactions
of the fuel molecules. Increase in length of carbon chains is known
to improve the ignition quality of alcohol molecules which in-turn
influences the ignition delay. Ignition delay decreases with an
increase in carbon chain length which is partly due to the increase
in the number of secondary C–H bonds and the greater ability of
the fuel peroxy radicals to isomerize [59]. Though the oxygen
content of higher alcohols decreases with increase in number of
carbon atoms (as seen from Fig. 2), the hydroxyl (–OH) radicals
would still populate fuel-rich regions and would help the unsatu-
rated HC species to get oxidized instead of participating in soot
growth reactions [60]. This fuel-borne oxygen strongly influences
the combustion behavior through local air/fuel ratio in various
zones and affects in-cylinder temperature and emission formation
[61,62]. The kinematic viscosity and density of the test fuels
 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256 249

Table 3
Properties of test fuels.

Properties Test method ULSD ISB30 PEN30 HEX30 OCT30

Oxygen (wt%) – 0 6.378 5.25 4.71 3.69
Volumetric energy density (MJ/m3) – 36852.6 32481.9 33715.2 34549.0 34997.9
Calculated cetane index ASTM D4737 52 40.9 42.4 43.3 46.5
Low heating value (MJ/kg) ASTM D240 43.356 38.854 40.233 41.12 41.542
Kinematic viscosity at 40 °C (mm2/s) ASTM D445 3.522 3.245 3.321 3.86 4.74
Density (kg/m3) ASTM D4052 850 836 838 840.2 842.47
Flash point (°C) ASTM D93 72 28 49 63 70

purposes in India. The existing population of these diesel driven

pump-sets in the country is about 14.42 million [65]. According
to a survey carried out by the Indian Petroleum Conservation
Research Association (PCRA), the annual production of diesel
driven pump-sets is 1.5 million with an expected annual growth
of 7%. This sector recorded a consumption of 6 MMT (Million
Metric Tons) of diesel which is about 8.55% of India’s total diesel
consumption (69 MMT) in the year 2012–2013 [66]. Nevertheless,
a large population of farmers in India are severely exposed to toxic
diesel exhaust emanating from these stationary equipment. Hence
this engine is chosen for this study. Specifications of this engine are
given in Table 4.
The schematic diagram of the experimental setup is depicted in
Fig. 3. A swinging field electrical dynamometer was used to apply
the load on the engine. This electrical dynamometer consists of a
5-kVA AC alternator (220 V, 1500 rpm) mounted on bearings and
Fig. 2. Comparison of ASTM properties (expressed as dimensionless numbers) of on a rigid frame for a swinging field type loading. The output
higher alcohols.
power was obtained by measuring the reaction torque using a
strain gauge type load cell. The pressure inside the combustion
Table 4 chamber was measured using an AVL GH12D miniature pressure
Engine specifications. transducer connected to an AVL3066A02 Piezo Charge Amplifier.
The crank angle and the position of top dead center (TDC) were
Make and model Kirloskar, TAFI make
measured using an AVL364 Angle Encoder. The charge amplifier
Number of cylinders One
and the encoder were connected to an AVL 615 Indimeter A/D card,
Bore 87.5 mm
Stroke 110 mm
which converts analog input to digital output. Al/Cr K-type ther-
Swept volume 661 cm3 mocouple was used to measure the exhaust gas temperature.
Clearance volume 36.87 cm3 AVL 615 Indimeter software was used to analyze the output data
Compression ratio 17.5:1 from the A/D card. This generates a pressure-crank angle diagram
Rated output 4.4 kW at 1500 rpm
that indicates the variation of pressure and heat release rate at
Rated speed 1500 rpm
Injection type Direct injection every crank angle and also indicates the crank angles at which
Injection pressure 210 bar the combustion starts and the percentage (10%, 50%, & 90%) of heat
Fuel injection timing 23°CA bTDC released during the combustion. Measurements of all these param-
Fuel injection duration 20–30°CA
eters were carried out for 100 cycles and the average value of these
cycles was recorded as a measured parameter at that load.
Start of fuel injection (SOI) was determined at static conditions
increases in the order: ISB30 < PEN30 < HEX30 < OCT30, which
using the spill method. The fuel injection pump outlet was discon-
implies the spray and atomization characteristics of test fuels is
nected and connected to an annular tube specially designed for this
better when the number of carbon atoms decreases. High viscosity
purpose. By slowly rotating the flywheel, fuel was made to spill out
is also advantageous in reducing the wear of moving parts in the
from the tube. The flywheel was provided with divisions on its
fuel systems and in the engine. The calorific value of the blends
circumference. The distance of the spill out point from the TDC
increases with an increase in carbon number as seen from Fig. 2.
position on flywheel was converted into degrees as the start of fuel
Though the latent heat of vaporization of alcohols decreases with
injection angle. While this method of SOI measurement gives
increase in its carbon content, it is generally higher than diesel
acceptable relative results, it should be noted that it is not possible
(From Table 1). Therefore when it vaporizes, more heat is absorbed
to achieve absolute accuracy. A similar method was also used
from the surroundings and produces a cooling effect on the cylin-
earlier to determine the SOI of this engine [67]. NOx, HC and CO
der charge which might be beneficial in bringing down in-cylinder
emissions were measured using MRU Delta 1600L exhaust gas ana-
temperatures and in-turn NOx emissions [63,64]. However, charge
lyzer and smoke opacity was measured using AVL 439 opacimeter.
cooling also affects the ignition delay which may not be beneficial
with low cetane number fuels.
2.3. Error analysis
2.2. Test engine and facilities
Errors and uncertainties in the experiments can arise from
Tests were performed in a naturally-aspirated, constant-speed instrument selection, condition, calibration, environment, observa-
(1500 rpm), single-cylinder, four-stroke, direct-injection diesel tion, reading and test planning [68]. Therefore, it is necessary to
engine which is widely used to drive pump-sets for irrigation establish the accuracy of the experiments by carrying out an error
250 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256

Fig. 3. Schematic of the experimental setup.

Table 5
Range, accuracy and percentage uncertainties of instruments used.

Instrument Measured quantity Range Accuracy Uncertainties, %

Gas analyzer NOx 0–5000 ppm ±10 ppm 0.20
HC 0–20,000 ppm ±20 ppm 0.20
CO 0–20% ±0.02% 0.15
Opacimeter Smoke opacity 0–100% ±1% 1.00
Speed measuring unit Engine speed 0–9999 rpm ±10 rpm 0.15
Pressure transducer Cylinder pressure 0–250 bar ±0.1 bar 0.10
Crank angle encoder Crank angle 0–360° ±1° 0.20

analysis. The magnitudes of error in various measured parameters
namely speed, pressure, crank angle and exhaust emissions were
estimated from the minimum values of output and accuracy of
the instruments using the root-mean square method [69,70].
Table 5 shows the range, accuracy and uncertainties of the instru-
ments used in this study.
2.4. Test procedure
All the tests were conducted under steady state conditions. No
modifications were made to the test engine. Since the calorific
value and oxygen contents of the test fuels vary, the comparison
between them was effected at the same load, i.e. brake mean effec-
tive pressure (BMEP) and not at the same fuel injection rates or
air/fuel ratio. The temperature of the lubricating oil was main-
tained between 85 and 90 °C. The engine was operated at the man-
ufacturer recommended injection timing of 23°CA before top dead
center (bTDC) and the injection pressure was kept constant at
210 bar throughout the study. There is a single-main injection in
which the fuel injection duration is varied between 20 and 30°CA
in order to produce the same work output under varying load con-
ditions. The engine was warmed up for 10 min to allow for stabi-
lization before the readings were recorded. In each test, the
combustion data generated from the AVL 615 Indimeter software,
exhaust smoke and oxides of nitrogen only were recorded. For each
engine operating point and test fuel blend, the measurements were
repeated three times and the mean value was reported. The coeffi-
cient of variance (standard deviation divided by the mean value)
for all reported quantities was found to be less than 3% which sig-
nifies that the measurements were repeatable within the experi-
mental uncertainties. At first, the engine was run with diesel fuel
which forms the reference fuel for this study. The baseline data
was recorded. Before refueling, the engine was allowed to run for
some time in-order for it to consume the fuel that remained in
the fuel system during the previous trial. Later the engine was
run with the next test fuel.
3. Results and discussion
The results of the combustion and emission characteristics are
presented and discussed for higher alcohol/diesel blends with ref-
erence to baseline diesel operation. Some results were analyzed
only at high load conditions for the sake of brevity of space of this
paper and also because the fuel/air mixture has longer residence
time at low speed and high load conditions.
3.1. Combustion analysis
Combustion characteristics were analyzed based on in-cylinder
pressure measurements. HRRs were deduced from the pressure
data that is averaged over 100 cycles to minimize the effect of
cycle-to-cycle variations. Ignition delay is actually the time lag
between the SOI and the start of combustion when the fuel–air
mixture is ignited. However due to vaporization effects, the apparent
HRR curve will exhibit negative values before combustion. The
start of combustion is taken as the crank angle at which the apparent
HRR changes from negative to positive. Hence, the SOI is taken as
the crank angle (CA) at which the nozzle needle lifts by 5%. Fig. 4
shows in-cylinder pressure and HRR profiles for all test fuels at
high engine load that corresponds to the BMEP of 5.3 bar.
One can observe from Fig. 4 that the ignition delay of ISB30
stands out from the other test fuels. Iso-butanol has the longest
ignition delay due to its lowest cetane number among all alcohols.
 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256
Fig. 4. Variations of (a) in-cylinder pressure versus crank angle and (b) HRR versus crank angle for all test fuels at BMEP = 5.3 bar and speed = 1500 rpm.
Degree of branching in alcohols also affects the ignition delay.
Higher the degree of branching, longer the ignition delay is. This
is due to slower H-abstraction and inhibition of isomerization in
branched chain alcohols (like iso-butanol in Fig. 1) that increases
the ignition delay when compared to straight chain alcohols [59].
It can be observed from Fig. 4 that the order of ignition delay is
(from shortest to longest): ULSD, OCT30, HEX30, PEN30 and
ISB30. This order directly correlates to the lowering cetane number
from ULSD through ISB30 as seen in Table 3. Earlier studies have
reported a decrease in ignition delays with increasing carbon chain
length for all functional groups [71,72].
At the end of the ignition delay, the ‘‘premixed combustion’’
consumes most of the vaporized fuel present in the combustion
chamber. The ability of the fuel to mix well with air and burn is
manifested in the form of cylinder pressure. High peak pressure
and maximum rate of pressure rise correspond to a large amount
of fuel burnt during the premixed combustion phase [73]. ISB30
exhibits highest peaks of in-cylinder pressure and HRR as inferred
from Fig. 4. The sequence of peak pressure and HRR for the test
fuels is (from highest to lowest): ISB30 > PEN30 > HEX30 >
OCT30 > ULSD.
Premixed combustion phasing mainly depends on the time
available for air–fuel mixing before ignition. As mentioned earlier,
long ignition delay is a characteristic of alcohol combustion due to
its low cetane number. Therefore, more quantity of fuel gets
Fig. 5. (a) Mass fraction burned (MFB) as a function of crank angle and (b) Shape factor ‘m’ of Wiebe function for all test fuels at BMEP = 5.3 bar and speed = 1500 rpm.
251
injected into the cylinder during this delay period. As a result,
ISB30 shows an enhanced premixed combustion phase due to its
longest ignition delay among other test fuels. The low viscosity
of ISB30 also leads to better fuel atomization and spray character-
istics. Peak in-cylinder pressure and peak HRR generated by the
test fuels are of the following order (from highest to lowest):
ISB30 > PEN30 > HEX30 > OCT30 > ULSD.
In this study, CA10 implies the crank angle at which 10% of the
mass fraction is burned and MFB10 indicates the percentage of
mass fraction burned up to 10°CA from the start of combustion.
Fig. 5a shows the percentage of mass fraction burned (MFB) as a
function of crank position for all higher alcohol/diesel blends at
BMEP = 5.3 bar. Wiebe’s function, which is most commonly used
in engine modeling, is employed to estimate the mass fraction
burned as a function of crank position. It is expressed as shown
in Eq. (1),
n
mþ1 o
hh i
a Dhc
x¼1e ð1Þ
where Dhc is the combustion duration in crank angle degree, h is the
instantaneous crank angle, hi is the crank angle degree at the start of
combustion, a is the parameter that characterizes the completeness
of combustion (for MFB = 90%, a = 2.3026), and m is the shape
factor that signifies the rate of combustion which is expressed as
in Eq. (2),
252 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256

0:1
ln 0:9 Table 6
m ¼ f ðh10  h90 Þ ¼   ð2Þ Combustion parameters for all test fuels at BMEP = 5.3 bar and speed = 1500 rpm.
ln hh90
10
hi
hi
Test CD ID m IMEP ROPR Pmax HRRmax
fuel (°) (°) (–) (bar) (bar/°) (bar) (J/°)
It is characterized by a S-shaped curve as seen in Fig. 5a in which
the burning rate of fuel/air mixture increases from ‘0’ as the com- ULSD 54.45 20.10 1.02 7.33 5.44 68.33 81.7
ISB30 47.20 22.95 0.92 8.09 8.98 75.63 148.9
bustion starts and tends exponentially to ‘1’ as the combustion ends
PEN30 48.60 21.15 0.92 7.82 8.17 74.81 106.9
[74]. The experimental mass fraction burned profiles were fitted HEX30 49.70 20.75 0.92 7.55 7.57 69.45 87.9
using the Wiebe’s function by defining the shape factor ‘m’ as a OCT30 54.10 20.55 0.95 7.47 5.91 69.38 86.5
function of CA10 and CA90 [75]. It can be seen that the burning rate
is highest at the start of combustion (SOC) for ISB30 which directly
correlates to its highest premixed heat release. The mass fraction HC species to get oxidized instead of participating in soot growth
burned for ULSD is the least. reactions. With the combustion assisted by the presence of fuel-
Fig. 5b compares the values of shape factor ‘m’ of Wiebe’s func- bound oxygen, higher fraction of alcohol in the blends causes lower
tion for ULSD and higher alcohol/diesel blends which signifies rate smoke opacity. Fig. 7a portrays the variations of smoke opacity as a
of combustion. Small values of ‘m’ implies higher burning rate dur- function of engine load for all test fuels. It is clearly discernible that
ing the SOC while large values of ‘m’ denotes a higher rate at the ISB30 blend presents the lowest smoke emissions due to its highest
end of combustion [76]. The values of ‘m’ as seen from Fig. 5b for oxygen content among the other alcohols (From Table 3). As the
ISB30, PEN30 and HEX30 are almost similar which indicates that number of carbon atoms in the alcohol increases, its oxygen
their burning rate is higher at the SOC. The value of ‘m’ for ULSD percentage decreases (from Fig. 2). Thus smoke opacity of the
is high which denotes a higher burning rate at later stages of com- blends was found to be in the order (highest to lowest):
bustion. It can be inferred from Fig. 5b that the order of higher pre- ULSD > OCT30 > HEX30 > PEN30 > ISB30.
mixed heat release at the SOC is (from highest to lowest):
ISB30 > PEN30 > HEX30 > OCT30 > ULSD. 3.2.2. NOx emissions
Fig. 6 shows the overall combustion progression for all test fuels There are generally three accepted mechanisms for NOx forma-
at high engine load condition. Combustion duration (CD) is taken tion: thermal NOx, prompt NOx and fuel NOx [77,78] Thermal NOx
as the duration between start of combustion and 90% cumulative is formed by the high-temperature reaction of nitrogen with oxy-
heat release. For instance, CD for OCT30 blend is shown as gen, by the well-known Zeldovich mechanism [79]. Prompt NOx
MFB90 in Fig. 6. The mass fractions of fuel burned at various crank is formed by relatively faster reaction between nitrogen, oxygen,
angles are shown in colored stripes. For instance, the mass fraction and hydrocarbon radicals [80]. It is generally an important mecha-
burned between CA50 and CA90 is represented as a dark-red- nism in low temperature combustion processes but much less
colored stripe in Fig. 6. A quicker look shows that the combustion important when compared to thermal NOx in high temperature
duration for ISB30 is shortest. As discussed earlier, longer ignition environments. Thermal NOx formation is highly dependent on
delays promote fuel–air mixing that leads to higher premixed com- the in-cylinder temperature, oxygen concentration and the resi-
bustion fraction. The CD for ISB30 is shortest because of faster dence time of gases during combustion [81]. Fuel NOx is formed
burning of more premixed charge after the long ignition delay. by the direct oxidation of organo-nitrogen compounds contained
Hence fuels with longer ignition delay presented shorter CD [58]. in the fuel. Fig. 7b shows the variations of NOx emissions as a func-
The sequence of CD for all test fuels is (from shortest to longest): tion of engine load for ULSD and all higher alcohol/diesel blends.
ISB30 < PEN30 < HEX30 < OCT30 < ULSD. Zheng et al. [58] have Nitric oxide (NO) and nitrogen dioxide (NO2) are together referred
previously reported iso-butanol/diesel blends with higher blending to as NOx. In case of ISB30, it can be seen that NOx emissions gen-
ratios to present shorter CD. Table 6 quantitatively summarizes the erally decreases with increasing iso-butanol content in the blends.
combustion parameters for all test fuels at BMEP = 5.3 bar and This is due to the engine running leaner and the dominant influ-
speed = 1500 rpm. ence of lower calorific value and higher latent heat of vaporization
of iso-butanol causing a cooling effect that reduces in-cylinder
3.2. Emission analysis temperature leading to less NOx. Similar NOx behavior was
reported earlier with iso-butanol [37,38,40]. The domination of
3.2.1. Smoke opacity higher latent heat of vaporization over lower cetane number is dis-
Alcohols are oxygenated compounds with hydroxyl radicals cernible with PEN30 and HEX30 blends only at low/medium loads.
that populate even locally fuel-rich zones and help the unsaturated At high loads, NOx emissions are higher than that of ULSD case.

Fig. 6. Overall combustion progression for all test fuels at BMEP = 5.3 bar and speed = 1500 rpm.
 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256 253

Fig. 7. Variations of (a) Smoke opacity and (b) NOx emissions for all test fuels as a function of engine load.

Fig. 8. Variations of (a) HC and (b) CO emissions for all test fuels as a function of engine load.

There is a shift in this dominance as more quantity of fuel is
injected into the cylinder to produce a higher BMEP. Lower cetane
number of PEN30 and HEX30 causes an ignition delay during
which more quantity of fuel is injected and the high oxygen con-
tent results in higher combustion temperatures which eventually
leads to high NOx. Similar NOx behavior with n-pentanol was
reported earlier [41,43–46]. In the case of OCT30, the cooling effect
of higher latent heat of vaporization is predominant over the effect
of lower cetane number and oxygen content [82]. This is because of
the higher cetane number and lower oxygen content of n-octanol
that causes a shorter ignition delay and lower combustion temper-
atures. In summary, NOx emissions of the higher alcohol/diesel
blends are in the order of (highest to lowest), at low/medium
loads: ULSD > OCT30 > HEX30 > PEN30 > ISB30 and at high loads:
PEN30 > HEX30 > ULSD > OCT30 > ISB30.
3.2.3. HC emissions
Fig. 8a shows the variations of HC emissions as a function of
engine load for all higher alcohol/diesel blends in comparison to
ULSD. Several factors are related to the formation of HC emissions
for alcohol/diesel blends in diesel engines. Firstly, the lower cetane
number of alcohols deteriorates self-ignition characteristics of
the blends and promotes a quenching effect in the leaner mixture
zone of the cylinder that increases HC emissions [37]. Secondly, the
higher heat of evaporation of alcohols causes slower and poorer
fuel–air mixing which increases HC emissions [38]. Thirdly, the
higher oxygen content of the alcohol/diesel blends lowers HC
emissions by favoring oxidation of unburned hydrocarbons at
relatively high in-cylinder temperatures [43]. All these factors
counter-act with each other and HC emissions eventually increase
or decrease as a result of their combined effect.
High HC emission of iso-butanol/diesel blends is attributed to
the dominative effect of latent heat of evaporation over its cetane
number [38]. However, for n-pentanol/diesel blends, the increase
in HC emissions is attributed to the dominative effect of the cetane
number of n-pentanol which allowed more time for the fuel to
vaporize, leading to a broader lean outer flame zone. In this case,
the heat of evaporation had only slight influence on HC emissions
[43]. From Table 1, it can be deduced that, with an increase in car-
bon number, the latent heat of evaporation of alcohols gradually
decreases and cetane number gradually increases. Therefore, as
the alcohol gets higher, the dominative influence of latent heat of
evaporation over HC emissions weakens and the effect of cetane
number takes over.
From Fig. 8a, it can be seen that HC emissions decrease gradu-
ally as the alcohol gets higher because of the increasing cetane
number that allows only less time for the fuel to vaporize during
the shortened ignition delay period. HC emissions are lowest for
254 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256
Table 7
Comparative summary of combustion and emission characteristics for all test fuels.
Characteristics Parameter
Combustion Ignition delay (longest to shortest)
Peak pressure (highest to lowest)
Peak HRR (highest to lowest)
Combustion duration (longest to shortest)
Emissions Smoke opacity (highest to lowest)
NOx emissions (highest to lowest) at high load
NOx emissions (highest to lowest) at low/medium load
HC emissions (highest to lowest)
CO emissions (highest to lowest)
n-octanol/diesel blends as a result of the combined effect of a
slightly longer ignition delay, as seen from Fig. 4a and higher
oxygen content of n-octanol when compared to ULSD. The oxygen
content of OCT30 also promotes the oxidation of hydrocarbons and
helps lowering the HC emissions. In summary, HC emissions of the
higher alcohol/diesel blends are in the order of (highest to lowest):
ISB30 > PEN30 > ULSD > HEX30 > OCT30.
3.2.4. CO emissions
The variations of CO emissions as a function of engine load for
all higher alcohol/diesel blends in comparison to ULSD are depicted
in Fig. 8b. CO emissions follow the trend of smoke emissions which
can be attributed to the high oxygen content of the blends that pro-
motes the oxidation of carbon monoxide. ISB30 shows highest
reductions due to its highest oxygen content among all the blends.
CO emissions of the blends were found to be in the order (highest
to lowest): ULSD > OCT30 > HEX30 > PEN30 > ISB30.
A comparative summary of combustion and emission character-
istics of all test fuels is presented in Table 7.
4. Conclusions
This study was intended to compare and analyze the effects of
some higher alcohol/diesel blends on combustion and emission
characteristics of a DI diesel engine. Four test blends containing
30 vol% of iso-butanol, n-pentanol, n-hexanol and n-octanol (desig-
nated as ISB30, PEN30, HEX30 and OCT30, respectively) were
prepared on an individual basis for this purpose and the following
conclusions were drawn based on the experimental results with
respect to ULSD:
1. ISB30 experienced the longest ignition delay due to its lowest
cetane number among all alcohols. It’s branched chain structure
also contributed to this delay as a result of slower H-abstraction
and inhibition of isomerization in branched-chain alcohols
when compared to straight-chain alcohols. The order of ignition
delay is (from shortest to longest): ULSD < OCT30 < HEX30
< PEN30 < ISB30.
2. ISB30 exhibited highest peaks of in-cylinder pressure and HRR
compared to other test fuels. The sequence of peak pressure
and HRR for the test fuels is (from highest to lowest):
ISB30 > PEN30 > HEX30 > OCT30 > ULSD.
3. The burning rate of ISB30 is higher at the start of combustion
which correlates to its higher premixed heat release. The
amount of premixed heat release at the start of combustion
for the test fuels, as estimated using Wiebe’s function is of the
order (from highest to lowest): ISB30 > PEN30 > HEX30 > OCT30
> ULSD.
4. The combustion duration for ISB30 is shortest because of the
faster burning of more premixed charge after the longest igni-
tion delay. The combustion duration for all test fuels is in the
sequence (from shortest to longest): ISB30 < PEN30 < HEX30
< OCT30 < ULSD.
Order
ISB30 > PEN30 > HEX30 > OCT30 > ULSD
ISB30 > PEN30 > HEX30 > OCT30 > ULSD
ISB30 > PEN30 > HEX30 > OCT30 > ULSD
ULSD > OCT30 > HEX30 > PEN30 > ISB30
ULSD > OCT30 > HEX30 > PEN30 > ISB30
PEN30 > HEX30 > ULSD > OCT30 > ISB30
ULSD > OCT30 > HEX30 > PEN30 > ISB30
ISB30 > PEN30 > ULSD > HEX30 > OCT30
ULSD > OCT30 > HEX30 > PEN30 > ISB30
5. Smoke opacity is low for all higher alcohol/diesel blends due to
their oxygenated nature. It was found to be in the order (highest
to lowest): ULSD > OCT30 > HEX30 > PEN30 > ISB30.
6. NOx emissions decreased for all higher alcohol/diesel blends at
low/medium loads. However, it is higher than ULSD for PEN30
and HEX30 at high engine loads. NOx emissions of higher alcohol/
diesel blends are in the order (highest to lowest) at low/med-
ium loads: ULSD > OCT30 > HEX30 > PEN30 > ISB30 and at high
load: PEN30 > HEX30 > ULSD > OCT30 > ISB30.
7. HC emissions of the higher alcohol/diesel blends are in the
order of (highest to lowest): ISB30 > PEN30 > ULSD > HEX30 >
OCT30. CO emissions of the blends were found to be in the
order (highest to lowest): ULSD > OCT30 > HEX30 > PEN30
> ISB30.
Acknowledgements
The authors appreciate the support of the Management of Sri
Venkateswara College of Engineering and Jeppiaar Institute of
Technology, Sriperumbudur, Chennai, TN, India for facilitating this
research. The authors acknowledge the assistance rendered by
Polymeric Materials Research Lab at Alagappa College, Karaikudi,
TN, India for estimating fuel properties.
References
[1] Rajesh Kumar B, Saravanan S. Use of higher alcohol biofuels in diesel engines: a
review. Renew Sustain Energy Rev 2016;60:84–115. http://dx.doi.org/10.1016/
j.rser.2016.01.085.
[2] Rasskazchikova TV, Kapustin VM, Karpov SA. Ethanol as high–octane additive
to automotive gasolines. Production and use in Russia and abroad. Chem
Technol Fuels Oils 2004;40(4):203–10. http://dx.doi.org/10.1023/
b:cafo.0000041215.14876.ce.
[3] Doğan O. The influence of n-butanol/diesel fuel blends utilization on a small
diesel engine performance and emissions. Fuel 2011;90(7):2467–72. http://dx.
doi.org/10.1016/j.fuel.2011.02.033.
[4] Campos-Fernández J, Arnal JM, Gómez J, Dorado MP. A comparison of
performance of higher alcohols/diesel fuel blends in a diesel engine. Appl
Energy 2012;95:267–75. http://dx.doi.org/10.1016/j.apenergy.2012.02.051.
[5] Akhtar MK, Dandapani H, Thiel K, Jones PR. Microbial production of 1-octanol:
a naturally excreted biofuel with diesel-like properties. Metab Eng Commun
2015;2:1–5. http://dx.doi.org/10.1016/j.meteno.2014.11.001.
[6] Heuser B, Mauermann P, Wankhade R, Kremer F, Pischinger S. Combustion and
emission behavior of linear C8-oxygenates. Int J Engine Res 2015;16
(5):627–38. http://dx.doi.org/10.1177/1468087415594951.
[7] Sarathy SM, Oßwald P, Hansen N, Kohse-Höinghaus K. Alcohol combustion
chemistry. Prog Energy Combust Sci 2014;44:40–102. http://dx.doi.org/
10.1016/j.pecs.2014.04.003.
[8] Popuri SSS, Bata RM. A performance study of iso-butanol-, methanol-, and
ethanol-gasoline blends using a single cylinder engine. SAE Technical Paper #
2953. 1993. http://dx.doi.org/10.4271/932953.
[9] Atsumi S, Hanai T, Liao JC. Non-fermentative pathways for synthesis of
branched-chain higher alcohols as biofuels. Nature 2008;451(7174):86–9.
http://dx.doi.org/10.1038/nature06450.
[10] Marcheschi RJ, Li H, Zhang K, Noey EL, Kim S, Chaubey A, et al. A synthetic
recursive ‘‘+1” pathway for carbon chain elongation. ACS Chem Biol 2012;7
(4):689–97. http://dx.doi.org/10.1021/cb200313e.
[11] Zhang K, Sawaya MR, Eisenberg DS, Liao JC. Expanding metabolism for
biosynthesis of nonnatural alcohols. Proc Natl Acad Sci 2008;105
(52):20653–8. http://dx.doi.org/10.1073/pnas.0807157106.
 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256
[12] Baez A, Cho K-M, Liao JC. High-flux isobutanol production using engineered
Escherichia coli: a bioreactor study with in-situ product removal. Appl
Microbiol Biotechnol 2011;90(5):1681–90. http://dx.doi.org/10.1007/s00253-
011-3173-y.
[13] Kondo T, Tezuka H, Ishii J, Matsuda F, Ogino C, Kondo A. Genetic engineering to
enhance the Ehrlich pathway and alter carbon flux for increased isobutanol
production from glucose by Saccharomyces cerevisiae. J Biotechnol 2012;159
(1–2):32–7. http://dx.doi.org/10.1016/j.jbiotec.2012.01.022.
[14] Higashide W, Li Y, Yang Y, Liao JC. Metabolic engineering of Clostridium
cellulolyticum for production of isobutanol from cellulose. Appl Environ
Microbiol 2011;77(8):2727–33. http://dx.doi.org/10.1128/aem.02454-10.
[15] Li H, Opgenorth PH, Wernick DG, Rogers S, Wu T-Y, Higashide W, et al.
Integrated electromicrobial conversion of CO2 to higher alcohols. Science
2012;335(6076). http://dx.doi.org/10.1126/science.1217643. pp. 1596–1596.
[16] Blombach B, Riester T, Wieschalka S, Ziert C, Youn J-W, Wendisch VF, et al.
Corynebacterium glutamicum tailored for efficient isobutanol production. Appl
Environ Microbiol 2011;77(10):3300–10. http://dx.doi.org/10.1128/
aem.02972-10.
[17] Atsumi S, Higashide W, Liao JC. Direct photosynthetic recycling of carbon
dioxide to isobutyraldehyde. Nat Biotechnol 2009;27(12):1177–80. http://dx.
doi.org/10.1038/nbt.1586.
[18] Li S, Wen J, Jia X. Engineering Bacillus subtilis for isobutanol production by
heterologous Ehrlich pathway construction and the biosynthetic 2-
ketoisovalerate precursor pathway overexpression. Appl Microbiol
Biotechnol 2011;91(3):577–89. http://dx.doi.org/10.1007/s00253-011-3280-9.
[19] Dekishima Y, Lan EI, Shen CR, Cho KM, Liao JC. Extending carbon chain length
of 1-butanol pathway for 1-hexanol synthesis from glucose by engineered
Escherichia coli. J Am Chem Soc 2011;133(30):11399–401. http://dx.doi.org/
10.1021/ja203814d.
[20] Phillips JR, Atiyeh HK, Tanner RS, Torres JR, Saxena J, Wilkins MR, et al. Butanol
and hexanol production in Clostridium carboxidivorans syngas fermentation:
medium development and culture techniques. Bioresour Technol
2015;190:114–21. http://dx.doi.org/10.1016/j.biortech.2015.04.043.
[21] Machado HB, Dekishima Y, Luo H, Lan EI, Liao JC. A selection platform for
carbon chain elongation using the CoA-dependent pathway to produce linear
higher alcohols. Metab Eng 2012;14(5):504–11. http://dx.doi.org/10.1016/j.
ymben.2012.07.002.
[22] Moss JT, Berkowitz AM, Oehlschlaeger MA, Biet J, Warth V, Glaude P-A, et al.
An experimental and kinetic modeling study of the oxidation of the four
isomers of butanol. J Phys Chem A 2008;112(43):10843–55. http://dx.doi.org/
10.1021/jp806464p.
[23] Grana R, Frassoldati A, Faravelli T, Niemann U, Ranzi E, Seiser R, et al. An
experimental and kinetic modeling study of combustion of isomers of butanol.
Combust Flame 2010;157(11):2137–54. http://dx.doi.org/10.1016/
j.combustflame.2010.05.009.
[24] Togbé C, Mzé-Ahmed A, Dagaut P. Kinetics of oxidation of 2-butanol and
isobutanol in a jet-stirred reactor: experimental study and modeling
investigation. Energy Fuels 2010;24(9):5244–56. http://dx.doi.org/10.1021/
ef1008488.
[25] Sarathy SM, Vranckx S, Yasunaga K, Mehl M, Oßwald P, Metcalfe WK, et al. A
comprehensive chemical kinetic combustion model for the four butanol
isomers. Combust Flame 2012;159(6):2028–55. http://dx.doi.org/10.1016/
j.combustflame.2011.12.017.
[26] Frassoldati A, Grana R, Faravelli T, Ranzi E, Oßwald P, Kohse-Höinghaus K.
Detailed kinetic modeling of the combustion of the four butanol isomers in
premixed low-pressure flames. Combust Flame 2012;159(7):2295–311.
http://dx.doi.org/10.1016/j.combustflame.2012.03.002.
[27] Merchant SS, Zanoelo EF, Speth RL, Harper MR, Van Geem KM, Green WH.
Combustion and pyrolysis of iso-butanol: experimental and chemical kinetic
modeling study. Combust Flame 2013;160(10):1907–29. http://dx.doi.org/
10.1016/j.combustflame.2013.04.023.
[28] Togbé C, Halter F, Foucher F, Mounaim-Rousselle C, Dagaut P. Experimental
and detailed kinetic modeling study of 1-pentanol oxidation in a JSR and
combustion in a bomb. Proc Combust Inst 2011;33(1):367–74. http://dx.doi.
org/10.1016/j.proci.2010.05.003.
[29] Heufer KA, Sarathy SM, Curran HJ, Davis AC, Westbrook CK, Pitz WJ. Detailed
kinetic modeling study of n-pentanol oxidation. Energy Fuels 2012;26
(11):6678–85. http://dx.doi.org/10.1021/ef3012596.
[30] Heufer KA, Bugler J, Curran HJ. A comparison of longer alkane and alcohol
ignition including new experimental results for n-pentanol and n-hexanol.
Proc Combust Inst 2013;34(1):511–8. http://dx.doi.org/10.1016/j.
proci.2012.05.103.
[31] Tang C, Wei L, Man X, Zhang J, Huang Z, Law CK. High temperature ignition
delay times of C5 primary alcohols. Combust Flame 2013;160(3):520–9.
http://dx.doi.org/10.1016/j.combustflame.2012.11.018.
[32] Li Q, Tang C, Cheng Y, Guan L, Huang Z. Laminar flame speeds and kinetic
modeling of n-pentanol and its isomers. Energy Fuels 2015;29(8):5334–48.
http://dx.doi.org/10.1021/acs.energyfuels.5b00740.
[33] Togbé C, Dagaut P, Mzé-Ahmed A, Diévart P, Halter F, Foucher F. Experimental
and detailed kinetic modeling study of 1-hexanol oxidation in a pressurized
jet-stirred reactor and a combustion bomb. Energy Fuels 2010;24
(11):5859–75. http://dx.doi.org/10.1021/ef101255w.
[34] Yeung C, Thomson MJ. Experimental and kinetic modeling study of 1-hexanol
combustion in an opposed-flow diffusion flame. Proc Combust Inst 2013;34
(1):795–802. http://dx.doi.org/10.1016/j.proci.2012.06.163.
255
[35] Cai L, Uygun Y, Togbé C, Pitsch H, Olivier H, Dagaut P, et al. An experimental
and modeling study of n-octanol combustion. Proc Combust Inst 2015;35
(1):419–27. http://dx.doi.org/10.1016/j.proci.2014.05.088.
[36] Al-Hasan MI, Al-Momany M. The effect of iso-butanol-diesel blends on engine
performance. Transport 2008;23(4):306–10. http://dx.doi.org/10.3846/1648-
4142.2008.23.306-310.
[37] Karabektas M, Hosoz M. Performance and emission characteristics of a diesel
engine using isobutanol–diesel fuel blends. Renewable Energy 2009;34
(6):1554–9. http://dx.doi.org/10.1016/j.renene.2008.11.003.
[38] Ozsezen A, Turkcan A, Sayin C, Canakci M. Comparison of performance and
combustion parameters in a heavy-duty diesel engine fueled with iso-butanol/
diesel fuel blends. Energy Explor Exploit 2011;29(5):525–41. http://dx.doi.org/
10.1260/0144-5987.29.5.525.
[39] Gu X, Li G, Jiang X, Huang Z, et al. Experimental study on the performance of
and emissions from a low-speed light-duty diesel engine fueled with
n-butanol–diesel and isobutanol–diesel blends. Proc Instit Mech Eng, Part D:
J Automob Eng 2013;227(2):261–71. http://dx.doi.org/10.4271/2012-28-0011.
[40] Rajesh Kumar B, Saravanan S. Effect of iso-butanol addition to diesel fuel on
performance and emissions of a DI diesel engine with exhaust gas
recirculation. Proc Instit Mech Eng, Part A: J Power Energy 2015;230
(1):112–25. http://dx.doi.org/10.1177/0957650915617107.
[41] Rajesh Kumar B, Saravanan S. Effects of iso-butanol/diesel and n-pentanol/
diesel blends on performance and emissions of a DI diesel engine under
premixed LTC (low temperature combustion) mode. Fuel 2016;170:49–59.
http://dx.doi.org/10.1016/j.fuel.2015.12.029.
[42] Campos-Fernandez J, Arnal JM, Gomez J, Lacalle N, Dorado MP. Performance
tests of a diesel engine fueled with pentanol/diesel fuel blends. Fuel
2013;107:866–72. http://dx.doi.org/10.1016/j.fuel.2013.01.066.
[43] Wei L, Cheung CS, Huang Z. Effect of n-pentanol addition on the combustion,
performance and emission characteristics of a direct-injection diesel engine.
Energy 2014;70:172–80. http://dx.doi.org/10.1016/j.energy.2014.03.106.
[44] Li L, Wang J, Wang Z, Xiao J. Combustion and emission characteristics of diesel
engine fueled with diesel/biodiesel/pentanol fuel blends. Fuel
2015;156:211–8. http://dx.doi.org/10.1016/j.fuel.2015.04.048.
[45] Li L, Wang J, Wang Z, Liu H. Combustion and emissions of compression ignition
in a direct injection diesel engine fueled with pentanol. Energy
2015;80:575–81. http://dx.doi.org/10.1016/j.energy.2014.12.013.
[46] Rajesh Kumar B, Saravanan S. Effect of exhaust gas recirculation (EGR) on
performance and emissions of a constant speed DI diesel engine fueled with
pentanol/diesel blends. Fuel 2015;160:217–26. http://dx.doi.org/10.1016/
j.fuel.2015.07.089.
[47] Sundar R, Saravanan G. Influence of hexanol-diesel blends on constant speed
diesel engine. Thermal Science 2011;15(4):1215–22. http://dx.doi.org/10.
2298/tsci101001089s.
[48] McCormick RL, Ross JD, Graboski MS. Effect of several oxygenates on regulated
emissions from heavy-duty diesel engines. Environ Sci Technol 1997;31
(4):1144–50. http://dx.doi.org/10.1021/es9606438.
[49] Heuser B, Kremer F, Pischinger S, Julis J, Leitner W. Optimization of diesel
combustion and emissions with newly derived biogenic alcohols,” SAE Technical
Paper # 2013–01-2690. 2013. http://dx.doi.org/10.4271/2013-01-2690.
[50] Zhang T, Munch K, Denbratt I. An experimental study on the use of butanol or
octanol blends in a heavy duty diesel engine. SAE Technical Paper # 2015–24-
2491. 2015. http://dx.doi.org/10.4271/2015-24-2491.
[51] Deep A, Kumar N, Karnwal A, Gupta D, Vibhanshu V, Sharma A, Patel JS.
Assessment of the performance and emission characteristics of 1-octanol/
diesel fuel blends in a water cooled compression ignition engine. SAE Technical
Paper # 2014–01-2830. 2014. http://dx.doi.org/10.4271/2014-01-2830.
[52] Hoppe F, Heuser B, Thewes M, Kremer F, Pischinger S, Dahmen M, et al. Tailor-
made fuels for future engine concepts. Int J Engine Res 2016;17(1):16–27.
http://dx.doi.org/10.1177/1468087415603005.
[53] Qureshi N, Blaschek H. Recent advances in ABE fermentation: hyper-butanol
producing Clostridium beijerinckii BA101. J Ind Microbiol Biotechnol 2001;27
(5):287–91. http://dx.doi.org/10.1038/sj.jim.7000114.
[54] Lan EI, Liao JC. Microbial synthesis of n-butanol, isobutanol, and other higher
alcohols from diverse resources. Bioresour Technol 2013;135:339–49. http://
dx.doi.org/10.1016/j.biortech.2012.09.104.
[55] Shen CR, Lan EI, Dekishima Y, Baez A, Cho KM, Liao JC. Driving forces enable
high-titer anaerobic 1-butanol synthesis in Escherichia coli. Appl Environ
Microbiol 2011;77(9):2905–15. http://dx.doi.org/10.1128/aem.03034-10.
[56] Kolodziej R, Scheib J. Bio-isobutanol: The next-generation biofuel. 2012.
<www.hydrocarbonprocessing.com/Article/3081332/Bio-isobutanol-Thenext-
generation-biofuel.html>, [Accessed 16 March 2016].
[57] Pan L, Zhang Y, Tian Z, Yang F, Huang Z. Experimental and kinetic study on
ignition delay times of iso-butanol. Energy Fuels 2014;28(3):2160–9. http://
dx.doi.org/10.1021/ef4021069.
[58] Zheng Z, Li C, Liu H, Zhang Y, Zhong X, Yao M. Experimental study on diesel
conventional and low temperature combustion by fueling four isomers of
butanol. Fuel 2015;141:109–19. http://dx.doi.org/10.1016/j.fuel.2014.10.053.
[59] Koivisto E, Ladommatos N, Gold M. Systematic study of the effect of the
hydroxyl functional group in alcohol molecules on compression ignition and
exhaust gas emissions. Fuel 2015;153:650–63. http://dx.doi.org/10.1016/
j.fuel.2015.03.042.
[60] Glaude PA, Pitz WJ, Thomson MJ. Chemical kinetic modeling of dimethyl
carbonate in an opposed-flow diffusion flame. Proc Combust Inst 2005;30
(1):1111–8. http://dx.doi.org/10.1016/j.proci.2004.08.096.
256 B. Rajesh Kumar et al. / Energy Conversion and Management 119 (2016) 246–256
[61] Rakopoulos CD, Dimaratos AM, Giakoumis EG, Rakopoulos DC. Investigating
the emissions during acceleration of a turbocharged diesel engine operating
with bio-diesel or n-butanol diesel fuel blends. Energy 2010;35(12):5173–84.
http://dx.doi.org/10.1016/j.energy.2010.07.049.
[62] Cheng X-B, Hu Y-Y, Yan F-Q, Chen L, Dong S-J. Investigation of the combustion
and emission characteristics of partially premixed compression ignition in a
heavy-duty diesel engine. Proc Instit Mech Eng, Part D: J Automob Eng
2014;228(7):784–98. http://dx.doi.org/10.1177/0954407013513012.
[63] Tutak W, Lukács K, Szwaja S, Bereczky Á. Alcohol–diesel fuel combustion in the
compression ignition engine. Fuel 2015;154:196–206. http://dx.doi.org/
10.1016/j.fuel.2015.03.071.
[64] Bayraktar H. An experimental study on the performance parameters of an
experimental CI engine fueled with diesel–methanol–dodecanol blends. Fuel
2008;87(2):158–64. http://dx.doi.org/10.1016/j.fuel.2007.04.021.
[65] GOI (Government of India). Annual Report (2013–2014), Ministry of Petroleum
& Natural Gas, New Delhi, IndiaAvailable from: http://petroleum.nic.in/docs/
Annual_Report/AR13-14.pdf2014 [Accessed 16 March 2016].
[66] GOI (Government of India). Indian Petroleum and Natural Gas Statistics,
Economics and Statistics Division, Ministry of Petroleum & Natural Gas, New
Delhi, IndiaAvailable from: http://petroleum.nic.in/docs/pngstat.pdf2014.
Accessed 16 March 2016.
[67] Saravanan S, Nagarajan G, Sampath S. Combined effect of injection timing, EGR
and injection pressure in NOx control of a stationary diesel engine fuelled with
crude rice bran oil methyl ester. Fuel 2013;104:409–16. http://dx.doi.org/
10.1016/j.fuel.2012.10.038.
[68] Devaraj J, Robinson Y, Ganapathi P. Experimental investigation of
performance, emission and combustion characteristics of waste plastic
pyrolysis oil blended with diethyl ether used as fuel for diesel engine.
Energy 2015;85:304–9. http://dx.doi.org/10.1016/j.energy.2015.03.075.
[69] Holman JP. Experimental methods for engineers. 8th ed. New York: McGraw-
Hill; 2012.
[70] Coleman HW, Steele WG. Experimentation, validation, and uncertainty
analysis for engineers. 3rd ed. New York: John Wiley & Sons; 2009.
[71] Koivisto E, Ladommatos N, Gold M. The influence of various oxygenated
functional groups in carbonyl and ether compounds on compression ignition
and exhaust gas emissions. Fuel 2015;159:697–711. http://dx.doi.org/
10.1016/j.fuel.2015.07.018.
[72] Westbrook CK. Chemical kinetics of hydrocarbon ignition in practical
combustion systems. Proc Combust Inst 2000;28(2):1563–77. http://dx.doi.
org/10.1016/s0082-0784(00)80554-8.
[73] Sinha S, Agarwal AK. Combustion characteristics of rice bran oil derived
biodiesel in a transportation diesel engine. SAE Technical Paper ICES
2005;2006–1375. http://dx.doi.org/10.4271/2005-26-354.
[74] Yeliana Y, Cooney C, Worm J, Michalek DJ, Naber JD. Estimation of double-
Wiebe function parameters using least square method for burn durations of
ethanol-gasoline blends in spark ignition engine over variable compression
ratios and EGR levels. Appl Therm Eng 2011;31(14–15):2213–20. http://dx.
doi.org/10.1016/j.applthermaleng.2011.01.040.
[75] Ghojel JI. Review of the development and applications of the Wiebe function: a
tribute to the contribution of Ivan Wiebe to engine research. Int J Engine Res
2010;11(4):297–312. http://dx.doi.org/10.1243/14680874jer06510.
[76] Alagumalai A. Combustion characteristics of lemongrass (Cymbopogon
flexuosus) oil in a partial premixed charge compression ignition engine.
Alexandria Eng J 2015;54(3):405–13. http://dx.doi.org/10.1016/j.aej.2015.03.
021.
[77] Kang Y, Wang Q, Lu X, Wan H, Ji X, Wang H, et al. Experimental and numerical
study on NOx and CO emission characteristics of dimethyl ether/air jet
diffusion flame. Appl Energy 2015;149:204–24. http://dx.doi.org/10.1016/j.
apenergy.2015.03.135.
[78] Kang Y, Lu X, Wang Q, Ji X, Miao S, Zong C, et al. An experimental and modeling
study of NOx and CO emission behaviors of dimethyl ether (DME) in a boiler
furnace. Fuel Process Technol 2014;122:129–40. http://dx.doi.org/10.1016/
j.fuproc.2014.01.030.
[79] Hossain S, Hossain MA. Numerical investigation of perfectly premixed
combustion and the effect of NOx emission for syngas in a gas turbine
combustor. In: ASME 2015 Power Conference Article # POWER2015-49388.
http://dx.doi.org/10.1115/power2015-49388.
[80] Baukal C. Everything you need to know about NOx. Met Finish 2005;103
(11):18–24. http://dx.doi.org/10.1016/s0026-0576(05)80816-5.
[81] Sayin C, Ilhan M, Canakci M, Gumus M. Effect of injection timing on the
exhaust emissions of a diesel engine using diesel–methanol blends. Renewable
Energy 2009;34(5):1261–9. http://dx.doi.org/10.1016/j.renene.2008.10.010.
[82] Rajesh Kumar B, Saravanan S, Rana D, Anish V, Nagendran A. Effect of a
sustainable biofuel – n-octanol – on the combustion, performance and
emissions of a DI diesel engine under naturally aspirated and exhaust gas
recirculation (EGR) modes. Energy Convers Manage 2016;118:275–86. http://
dx.doi.org/10.1016/j.enconman.2016.04.001.