Journal of the Energy Institute xxx (2014) 1e12

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Effects of higher ratios of n-butanol addition to dieselevegetable oil

blends on performance and exhaust emissions of a diesel engine
_
Alpaslan Atmanlı a, *, Erol Ileri a
, Bedri Yüksel b
a
Turkish Land Forces NCO Vocational College, Automotive Sciences Department, 10110 Balikesir, Turkey
b
Balikesir University, Department of Mechanical Engineering, 10145 Balikesir, Turkey

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

Article history: n-Butanol is a promising next generation alternative fuel for stabilizing diesel fuelevegetable oil blends
Received 6 July 2014 at low temperatures. In this study, the effects of higher n-butanol contents in diesel fuelevegetable oil
Received in revised form blends in a diesel engine were investigated. Ternary blends of diesel fuel (D)ecotton oil (CtO)en-butanol
10 September 2014
(nB) as percentages (vol.%) of 60%De10%CtOe30%nB (TB1), 50%De30%CtOe20%nB (TB2), 30%De30%CtO
Accepted 17 September 2014
Available online xxx
e40%nB (TB3), 30%De10%CtOe60%nB (TB4) and 20%De20%CtOe60%nB (TB5) were selected in the sol-
uble area of the ternary phase diagram for low temperature (
15  C) operability. The tests were con-
ducted employing each of the above ternary blends and diesel fuel, with the engine operating at full load
Keywords:
Renewable fuel and eight different engine speeds between 1800 and 4400 rpm. Increasing presence of n-butanol in the
n-Butanol blends improved density, kinematic viscosity and cold filter plugging point (CFPP), while deteriorated
Vegetable oil cetane number (CN) and heating value of the ternary blends. Experimental test results of ternary blends
Fuel properties showed that average brake torque, brake power, brake thermal efficiency (BTE) and exhaust gas tem-
Diesel engine perature decreased, while brake specific fuel consumption (BSFC) increased with increasing presence of
n-butanol in the blends. Addition of n-butanol to diesel fuelevegetable oil blends increased oxides of
nitrogen (NO and NO2) formations, while drastically decreasing formation of carbon monoxide (CO) and
hydrocarbon (HC) emissions. TB4 and TB5, which have the highest ratio of n-butanol, are promising
candidate for decreasing CO and HC emissions at the expense of increasing BSFC.
© 2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.

1. Introduction

Recently, the application of diesel engines which are widely used in fields like transportation and power has increased [1e4]. Similarly,
due to the rapid growth of diesel engines in the transportation and power sector, the consumption of diesel fuel keeps increasing as well. The
sharply rising crude oil prices at historically high levels have also boosted research on sustainable and renewable alternative fuel for diesel
engines with respect to the future availability of petroleum-based fuel reserves and environmental issues. The biomass based fuels can offer
a feasible solution to the world's dependence on petroleum-based fuel and can provide many advantages, such as environmental protection,
sustainability, and economical development [5,6].
Some types of alcohols and vegetable oils, which can be obtained from resources available locally within the country, are known to have
the potential of alternative diesel fuel in biofuels [2,3,7]. Vegetable oils can be obtained from edible and non-edible oilseed and have physical
characteristics close to those of diesel fuel and therefore behave like similar fuels. Behaving especially well is cottonseed oil, which is
classified as non-edible, is widely grown in Turkey and Greece [2,8,9]. The use of straight vegetable oils in diesel engines cause several
disadvantages related to their lower oxidation stability and volatility, higher viscosity and density. Among these disadvantages are carbon
deposit on injector and valve seat, clog fuel filters, poor fuel atomization and higher NOx emissions [8e10].
The legislated maximum levels of tailpipe emissions from diesel engines are becoming more stringent. In 1999, the Eurepon Uninon (EU)
adopted Directive 1999/96/EC, which introduced Euro III emission standards (2000), as well as Euro IV/V standards (2005/2008). Euro III
standards divided into two sub-stages: Stage III A and Stage III B. Stage III A emission standards for nonroad diesel engines introduce CO and

* Corresponding author. Tel.: þ90 266 2212350x4491; fax: þ90 266 2212358.
E-mail address: aatmanli@hotmail.com (A. Atmanlı).

http://dx.doi.org/10.1016/j.joei.2014.09.008
1743-9671/© 2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
2 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12

Nomenclature CO2 carbon dioxide

RH relative humidity
BSFC brake specific fuel consumption D diesel fuel
N2 nitrogen rpm revolutions per minute
BTDC before top dead center EN european norm
NO nitric oxide Ta temperature of the intake air
BTE brake thermal efficiency GExHW exhaust gas average molecular weights
NO2 nitrogen dioxide TB ternary blends
C centigrade Ha humidity of the intake air
NOx nitrogen oxides TS turkish standart
CFPP cold filter plugging point HC hydrocarbon
nB n-butanol VH cylinder volume
CtO cotton oil ISO international organization for standardization
O2 oxygen wt weight
CN cetane number kh,D correction factor for humidity
Pe brake power wR total percentage uncertainty
CO carbon monoxide mfc actual measured fuel consumption
ppm parts per million dp polar interaction parameter

NOx þ HC emission limits of 5.0 g/kWh and 4.7 g/kWh, respectively. In European countries, which have adopted Euro 5 emission standard for
their vehicles, Euro 6 emission standard will be implemented in 2014. Euro 6 emission standard requires the application of additional after
treatment technologies for decreasing tailpipe emissions especially NOx [11].
The main two methods for production of biofuels are transesterification and microemulsion. Transesterification method requires a
catalyst, heat (energy) and batch processing. In contrast, the microemulsion method has low production costs, simple and easy imple-
mentation, and minimal fuel processing [2,12e14]. Microemulsion can be used in diesel engines without engine modification, and chemical
reactions [12,14]. Therefore, microemulsion is an effective method where highly viscous vegetable oil is mixed with diesel fuel and alcohol
[14,15].
Many investigators have analyzed the effect of various alternative fuels and oxygenated additives of diesel engines for many years.
Recently, the most commonly examined oxygenated additives and its blending with diesel fuel are alcohols such as methanol and ethanol
[16,17]. Butanol suggests a better alternative fuel than ethanol and methanol considering its advantages [5,18]. Like ethanol, butanol is also a
bio-origin renewable fuel that can be produced by alcoholic fermentation of biomass, such as algae, corn, and other plant materials con-
taining cellulose that could not be used for food and would otherwise go to waste [18,19]. Butanol also can be produced by crude glycerol co-
product from the biodiesel production process [19].
Butanol's fuel properties such as hydrophobic, latent heat of vaporization and CN is closer to diesel fuel than lower alcohols [18,20,21].
Lower alcohols cause a longer ignition delay period of combustion because of their higher latent heat of vaporization compared to that of
diesel fuel. Compared to lower alcohols, low latent heat of vaporization and high heating content of n-butanol provides complete miscibility
with diesel fuel and shows better combustion characteristics in diesel engines [16,22e24]. In ethanolediesel blends instead of ethanol, the
usage of n-butanol demands neither a cetane enhancing additive nor a solubilizer due to its relatively high CN, high solubility and no phase
separation in diesel fuel [16,19,25,26]. As a result, butanol as a potential second generation biofuel is becoming a popular, competitive
alcohol in diesel engines [2,3,18,19,22,25].
Depending on the structure of diesel fuel and the system temperature, the solubility of a vegetable oil in diesel fuel changes. Phase
separation in the vegetable oil and diesel fuel mixtures is observed at relatively low temperatures, to prevent this situation, the micro-
emulsion method is used efficiently [13,14]. The presence of n-butanol in the blends prevents the phase stability of the vegetable oil and
diesel fuel mixtures and enhances fuel properties [3,18]. n-Butanol (dp ¼ 2.8) is a less polar molecule than ethanol (dp ¼ 4.3), and thus it
presents more miscibility with diesel fuel; this miscibility with vegetable oils operates excellently under various conditions [2,3,26,27]. n-
Butanol has already been used as a co-solvent in ethanolediesel and methanolediesel mixtures [28]. Because of its similarity to diesel fuel
properties, n-butanol is used mainly among the applicable co-solvents, which enables the use of n-butanolediesel mixtures in any pro-
portion [25e27].
The effect of diesel-n-butanol binary blends on engine performance and exhaust emissions in diesel engines were examined by many
researchers [16,19,22,25e27,29e33]. However, the open literature reports only a few papers concerning the effect of engine performance
and exhaust emissions of diesel engines fueled with diesel fuelevegetable oilen-butanol ternary blends.
The effect of croton megalocarpus oilen-butanolediesel fuel ternary blends on engine performance, combustion, and emission char-
acteristics are investigated by Lujaji et al. It was reported that fuel properties of vegetable oils were improved by the ternary blends [3,21].
Weerachanchai et al. reported that the mixture of palm kernel oil, diesel and n-butanol is a promising alternative diesel fuel to prevent the
problems related to the direct use of palm kernel oil. This study indicates that butanol as a cosolvent improved phase behavior charac-
teristics and fuel properties compared to ethanol [23]. Atmanli et al. examined the effect of diesel fuelecotton oilen-butanol ternary blends
on phase stability, engine performance and exhaust emissions in a diesel engine. They reported that the presence of n-butanol in ternary
blends enhanced solubility and low temperature behavior [34]. Diesel fuel-used palm oilen-butanol blends as alternative diesel fuel was
examined by Sharon et al. Increasing butanol content in the ternary blends reduced NOx, CO, CO2 and smoke emissions, while increased HC
emission and BTE [35]. As a result of these experimental studies, the next generation promising fuel, n-butanol, is safe and advantageous for
engine performance and exhaust emissions in diesel engines fueled with high blended ratios of n-butanol.

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12 3

Despite the many advantages mentioned above of n-butanol as an alternative diesel fuel, its blend with diesel fuel has not been qualified
in the wide range of operative conditions of diesel engines. Moreover, many researchers published recommendation with respect to effect of
binary and ternary blends containing n-butanol as an alternative diesel fuel in diesel engines and their stability at lower ambient tem-
peratures (
10  C,
25  C and
35  C) [2,3,5,15,21,34,36]. The mean ambient winter temperature in colder geographic areas (including
Turkey) of the world in January is approximately
15  C and the lower temperature phase stability of ternary blends was examined at that
temperature.
For that reason, this research is focused on the use of n-butanol as an additive in stabilizing cotton oil, which is an inedible oil grown
widely in Turkey [2,9], diesel blends. A ternary phase diagram at
15  C was plotted for determining the lower temperature phase stability
of the DeCtOenB system. Ternary blends, which were not examined in open literature, were selected in the soluble area of the ternary phase
diagram for low temperature operability. The main objective of this study was to investigate the influence of higher ratios of n-butanol
addition to diesel fuelecotton oil blends on engine performance and exhaust emissions of a diesel engine.

2. Materials and methods

2.1. Experimental facilities

The experiments were performed on a Land Rover turbocharged, direct injection, 110 type diesel engine, equipped with Bosch rotary
R509 mechanical fuel pump, following the Euro III emission standard. The main technical characteristics of the test engine are reported in
Table 1. A hydraulic-type (BT-190) dynamometer, with a maximum brake power of 119 kW, a maximum speed of 7500 rpm, a maximum
torque of 745 Nm, a load cell capacity of 2500 N, and a brake water pressure of 1e2 bar, coupled to the test engine was used as a loading
device. The fuel mass consumption was measured by Siemens MASS 6000 Ex-d transmitter with a resolution of 1 wt.%. The test fuel line was
reformed by adding a tank fueled with ternary blends, and a two-way, hand-operated control valve, which allowed rapid transferring from
diesel fuel to ternary blends. The engine speed, brake power, brake torque, fuel mass consumption, exhaust gas and cooling water tem-
peratures were displayed and controlled on the control panel. In order to automatically control the cooling water temperatures between 80
and 85  C, PT-100 temperature sensors were mounted on the inlet and outlet water pipes of the cooling water tank. Testo 350 exhaust gas
analyzer equipped with control unit was used for measuring CO, NO, NO2 and HC measurements in the range of 0e10,000 ppm,
0e4000 ppm, 0e500 ppm and 100e40,000 ppm, respectively.
The propagation of errors methodology was used to determine the uncertainties for the engine performance parameters. Eq. (1) shows
the total percentage uncertainty, wR of these calculated experimental values:
"
2
2
2 #12
vR vR vR
wR ¼ w þ w þ…þ wn (1)
vx1 1 vx2 2 vxn

where R is a given function of the independent variables x1, x2, … ,xn and w1, w2, … ,wn are the uncertainties of the independent variables
[37]. Table 2 reports the accuracy of the measurements and the uncertainties of the acquired quantities.

2.2. Test fuels

Low sulfur (0.035 wt.%) diesel fuel, cotton oil and n-butanol (analytical grade) were purchased from local commercial supplier and Merck,
respectively. The basic fuel properties of the diesel fuel, cotton oil, n-butanol and ternary blends were determined at the laboratories of
TUBITAK-MAM (The Scientific and Technological Research Council of Turkey-Marmara Research Center) and listed in Table 3.
In order to determine fatty acid compositions of cotton oil in agreement with the test method EN 15779 [38], an Agilent 6850 Network
gas chromatograph with HP-88 type column was used. The fatty acid composition of cotton oil is shown in Table 4.
Ternary phase behaviors were investigated by blending three components of DeCtOenB at
15  C. In order to determine the phase
boundaries of DeCtOenB system, cotton oil and diesel fuel or n-butanol, in blend ratios of 10/90, 20/80, 40/60, 50/50, 70/30 and 90/10 (by
wt.) were prepared, with 20 g samples accurately weighed using Sartorius BP121S type electronic scale with 0.1 mg precision. These
mixtures were kept at the constant temperature of
15  C via water bath (PolyScience 801 Heating Circulator). To form the ternary phase

Table 1
The basic technical specifications of the test engine.

Model Land Rover 110

Cylinder bore (mm) 90.47
Stroke (mm) 97
Volume (cm3) 2495
Compression ratio 19.5:1
Maximum torque (Nm) at 2200 rpm 235
Maximum power (kW) at 3800 rpm 82
Maximum speed (rpm) 4400 (þ40,
20)
Fuel injection system Turbocharged direct injection
Injection pump type Bosch Rotary R509
Injector type Bosch KBAL90P37
Injection pressure (kg/cm2) 200
Injection timing 15 BTDC
Turbocharge-delivered pressure (kg/cm2) 0.8e1
Emission standard Euro III

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
4 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12

Table 2
Accuracies of the measurements and the uncertainties in the calculated results.

Measured quantity Accuracy Calculated quantity Uncertainty (%)

Load ±0.03% Brake torque ±0.54
Speed ±1 rpm Brake power ±0.49
Time ±1% BSFC ±1.1
Temperature ±1  C BTE ±1.12
Humidity ±3 RH %
CO ±0.5 vol.%
NO ±0.5 vol.%
HC ±10 vol.%

diagram, n-butanol and diesel fuel were individually titrated in DeCtO and CtOenB, respectively, to achieve final visually homogeneous and
clear mixtures. At the end of the titration reaction, measurement of the dispensed titrant volume was taken to allow for calculation of the
analyte content based on the stoichiometry of the chemical reaction [34,39]. Calculated analyte and titrant volumes at
15  C were marked;
tie-line in red color (in the web version) which gives compositions within the soluble and insoluble phase regions in the ternary phase
diagram of the DeCtOenB system was plotted as seen in Fig. 1. Vegetable oilediesel fuel blends can form wax formations at ambient winter
temperatures in colder geographic areas because they contain straight and branched-chain hydrocarbons. Presence of wax formation in
carbon based fuels may plug the fuel filter or completely gel the fuel, making it impossible for the fuel system to deliver fuel to the engine
[8,40e42]. Fuels can be used effectively in a wide range of ambient temperatures. Fuel stability indicates the low temperature operability
limits of fuels. Especially in cold weather temperatures, fuels should be stable during long-term storage or fuel line delivery.
For this reason, ternary test blends, which were prepared by the splash-blending method [43], were selected in the soluble area of the
ternary phase diagram (marked with blue triangle (in the web version), denoted as TB1-5) of the DeCtOenB system at
15  C as shown in
Fig. 1. Physical appearance of the test fuels was single phase, homogeneous and clear.

2.3. Engine tests

Engine performance test procedure of TS 1231 [44] were followed for experiments under full load (100% throttle conditions) and the
engine speed variations were obtained by increasing the load in the BT-190 hydraulic-type dynamometer. Running of the engine outside
selected lower and upper engine speed limits is undesirable because of significant increases in exhaust emissions and decrease in brake
power. Before the engine performance and exhaust emission tests, technical specifications of the test engine were readjusted in accordance
with the Land Rover 110 catalog. During the engine tests, the cooling water temperature was stable between 80  C and 85  C via the PT-100
temperature sensors. The experiments started with a preliminary investigation of the engine fueled with either diesel fuel or ternary test
blends for 10 min to warm up, and then engine performance and exhaust emission tests were carried out. Following EN ISO 8178-6 test
standards [45], each exhaust emission test was performed on the same day to limit day to day deviations in the emission results because the
experiments are possibly affected by atmospheric humidity and temperature variations. In order to increase the reliability of the experi-
mental test results, the engine performance and exhaust emissions tests were operated and repeated three times and the results of the three
repetitions were averaged.

3. Results and discussions

3.1. Effect of component concentrations on phase behavior

The ternary phase diagram which is used in this study is an equilateral triangle which consists of three edges of three components
namely D, CtO and nB. Two edges at the bottom of triangle indicate diesel fuel and cotton oil mixtures at the left side and the right side,
respectively, while the peak of the triangle indicates the n-butanol mixture at a constant ratio for
15  C. The concentration value at each
point in the ternary phase diagram shows the volume percent of the three components (D, CtO and nB).
The solubility tie-line was plotted using titration values at
15  C as the boundary between single phase and two phase microemulsions.
As fuel is cooled, it reaches a temperature where it is no longer able to dissolve the waxy components that then begin to precipitate out of
the solution. Wax formation can also be exacerbated by blends of vegetable oil with diesel fuel [46].

Table 3
The basic fuel properties of test fuels.

Item D (vol.%) CtO nB Density (g/ml) Lower heating Cetane Kinematic viscosity CFPP ( C) Carbon Hydrogen Oxygen Stoichiometric
(vol.%) (vol.%) at 15  C value (Mj/kg) number (mm2/s) at 40  C (wt.%) (wt.%) (wt.%) airefuel ratio
Diesel fuel 100 e e 0.838 43.38 60.5 3.93
23 86.13 13.87 e 14.67
Cotton oil e 100 e 0.920 38.33 41.8 32.75
10 76.92 11.88 11.2 12.4
n-Butanol e e 100 0.810 33.10 17 2.63 <
51 64.82 13.60 21.58 11.19

TB1 60 10 30 0.827 39.80 42.6 2.90
23.1 80.80 13.07 6.13 13.47
TB2 50 30 20 0.848 39.77 43.7 4.97
18.7 79.05 12.48 8.47 12.97
TB3 30 30 40 0.846 37.79 36 4.98
20.3 77.58 12.37 10.05 12.69
TB4 30 10 60 0.824 36.75 31 2.90
32.5 77.20 12.88 9.92 11.3
TB5 20 20 60 0.834 36.27 29.7 3.81
31.2 76.37 12.48 11.15 12.55

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12 5

Table 4
Fatty acid composition of cotton oil.

Fatty acid composition (wt.%)

Saturated fatty acids
Myristic (C14:0) 0.79
Palmitic (C16:0) 23.13
Stearic (C18:0) 2.28
Arachidic (C20:0) 0.29
Behenic (C22:0) 0.51
Lignoceric (C24:0) 0.13
Unsaturated fatty acids
Palmitoleic (C16:1) 0.20
Oleic (C18:1) 19.08
Linoleic (C18:2) 52.50
Linolenic (C18:3) 0.22

Presence of higher ratio of 97 vol.% and 96 vol.% of diesel fuel and n-butanol in DeCtO and CtOenB mixtures presented a single phase
liquid system at
15  C respectively as shown in Fig. 1. However, to form a single phase microemulsion where cotton oil contents of 40 vol.%
in diesel fuel, required more than 15 vol.% n-butanol. In addition, presence of cotton oil higher than ratios of 40 vol.% in ternary blends
represented two phase microemulsions. It can be attributed to higher viscosity, cloud, pour and CFPP of cotton oil [8,9].
The cold flow properties such as CFPP of diesel fuel and n-butanol are
23  C and <
51  C, respectively. At cold weather conditions, all
engine fuels are required to be in clear and soluble liquid phase. Hence, the solubility of the CtOenB system was slightly better compared to
DeCtO system at
15  C temperature, because of better miscibility of n-butanol at low temperature. When Fig. 1 is considered, solubility
increased with the increase of n-butanol ratio in CtOenB system.
Because of low polarity and viscosity of n-butanol, all concentration of DenB mixtures in the ternary phase diagram (Fig. 1) depicted
single phase, as previously published in the literature [18,19,24e28,34]. This might indicate that the use of n-butanol could improve the fuel
solubility and forms a true solution in diesel fuel. Furthermore, in order to achieved a better solubility in diesel fuel, a higher amount of n-
butanol was required for cotton oil than diesel fuel.

3.2. Engine performance parameters

3.2.1. Brake torque and brake power

Fig. 2(a) and (b) show the variations of brake torque and brake power with respect to various engine speeds. From the bars of brake
torque and brake power in Fig. 2(a) and (b), it can be seen that the peak of brake torque and brake power values were obtained at 2200 rpm
and 3800 rpm, respectively and decreased with the engine speed increase. The maximum brake torque for diesel fuel, TB1-4 and TB5 at
2200 rpm were measured as 234.4, 212.5, 220.0, 209.2, 181.8 and 193.1 Nm, respectively. The average brake torque values of TB1-4 and TB5
decreased by 9.84, 6.34, 11.09, 22.67 and 21.37% respectively compared to that of diesel fuel. As can be seen Fig. 2(a), the presence of n-
butanol in the ternary blends corresponded to a greater decrease in the brake torque. It can also be observed from Fig. 2(a) that this reducing
effect was found to be very obvious with increasing n-butanol concentration when compared to those of the other test fuels, and was highest
with TB4. There were large decreases in the brake torque and brake power for TB4 and TB5 because of their lower heating values. As shown
in Table 3, the lower heating values of TB4 and TB5 are approximately 15.28% and 16.39% lower than that of diesel fuel. Compared to the
presence of n-butanol in the ternary blends, the addition of cotton oil to ternary blends had a positive impact on the brake torque and brake
power via its high heating content compared with that of n-butanol. The effect of high oxygen content of n-butanol caused the lower gas

Fig. 1. Ternary phase diagram of the DeCtOenB system at
15  C and selected ternary test blends.

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
6 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12

Fig. 2. Variation of brake torque (a), brake power (b) and BSFC (c) as a function of engine speed.

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12 7

temperature in the combustion chamber due to its higher latent heat of evaporation, which results in less brake torque and brake power
compared to cotton oil and diesel fuel [15,47]. A similar trend of brake torque was observed with brake power (Fig. 2(b)). The maximum
brake power was 74.9 kW for diesel fuel, 66.3 kW for TB1, 69.6 kW for TB2, 65.7 kW for TB3, 57.2 kW for TB4 and 56.6 kW for TB5. The
maximum and minimum reduction of average brake power values of TB4 and TB2 were 20.30 and 4.2%, respectively compared to that of
diesel fuel.

3.2.2. BSFC
BSFC is defined as Eq. (2) and its correlation with fuel properties of viscosity, density, lower heating value and CN.

BSFC ¼ mfc Pe (2)

where mfc and Pe are actual measured fuel consumption (g/h) and brake power (kW), respectively.
Fig. 2(c) depicts BSFCs of ternary blends and diesel fuel versus various engine speeds. BSFCs were especially noted to decrease between
maximum torque (2200 rpm) and power (3800 rpm) engine speeds for all test fuels in the range of 193.35 g/kWh (for diesel fuel) to
425.51 g/kWh (for TB4). From Fig. 2(c), it was observed that the test engine consumed higher ternary blends than diesel fuel to generate
equivalent brake power output for all test engine speeds due to lower heating value and higher latent heat of vaporization of n-butanol
[26,31], with the increasing presence of n-butanol in ternary blends led to greater increase in the BSFC. This increament is very obvious in
the case of fueling the engine with TB4 and TB5 because their net heating values drastically decrease (see Table 3) with the percentage of n-
butanol into ternary blends. The test results of BSFC for all ternary blends showed that increment in the average BSFC values was ordered as
TB4 > TB5 > TB3 > TB2 > TB1. Minimum BSFCs were obtained as 192.33, 248.19, 316.07, 303.01, 357.98 and 352.81 g/kWh for diesel fuel, TB1-
4 and TB5, respectively. The average BSFCs for usage of TB1-4 and TB5 were 29.39, 56.76, 58.39, 86.84 and 81.67% higher than those of diesel
fuel. Similar results were observed in the literature [3].

3.2.3. BTE
Thermal efficiency is a measure of the output work divided by the input energy in a thermal engine. Eq. (3) is applied for the calculate of
BTE,

BTE ¼ 3:6  106 be  Hu (3)

where be is brake specific fuel consumption (g/kWh) and Hu is lower heating value (kj/kg).
Fig. 3(a) illustrates the comparison of BTEs of diesel fuel and ternary blends as a function of engine speed. It can be seen in Fig. 3(a) that there
are noticeable difference with regards to BTEs between ternary blends and diesel fuel, especially where presence of n-butanol ratios in the
ternary blends are above 40 vol.%. Maximum and minimum BTEs of ternary blends were obtained at 3000 rpm as 36.45% for TB1 and at
4400 rpm as 16.17% for TB4. The reduction of the average BTEs of TB1-4 and TB5 are 15.49, 30.11, 26.98, 35.63 and 32.99% respectively compared
to that of diesel fuel. From these results, it can be interpreted that higher premixed combustion part possessed by the ternary blends because of
the lower heating value and CN of n-butanol (see Table 3), results in lower exhaust gas temperatures (see Fig. 3(b)) [19]. BTEs were increased
with an increase in cotton oil contents in ternary blends when compared to n-butanol, because of high heating content and CN of cotton oil.
Maximum BTEs were obtained with diesel fuel due to its lower BSFCs and higher heating content than all ternary blends.

3.2.4. Exhaust gas temperature

Changes in exhaust gas temperatures of diesel fuel and ternary blends as a function of engine speed are shown in Fig. 3(b). Diesel fuel
produced higher exhaust gas temperatures than all ternary blends under all test engine speeds. The highest exhaust gas temperatures of
diesel fuel, TB1-4 and TB5 were obtained at 486, 376, 391, 377, 343 and 350  C in the range of 3400e3800 rpm. Exhaust gas temperatures
measured by TB1-4 and TB5 decreased on average by 21.89, 20.51, 22.66, 29.25 and 27.48% compared to diesel fuel. It can be observed from
Fig. 3(b) that ternary blends produced lower exhaust gas temperatures than those of diesel fuel. The presence of more amount of oxygen in
the chemical structure of n-butanol may create a significant cooling effect of the fuel spray patterns leading to longer ignition delay, causing
incomplete combustion and lower exhaust gas temperatures. In ternary blends, high heating content and low latent heat of evaporation of
cotton oil caused higher exhaust gas temperature than that of n-butanol [15,40]. Also, it is supported by Rakopolos et al. [24] that n-butanol
produces a lower exhaust gas temperature because the engine runs overall ‘leaner’.
The turbocharger turbine is driven by the energy available in the engine exhaust and the turbocharger turbine speed increases with an
increase in exhaust gas temperature. The low exhaust gas temperature of ternary blends, especially TB4 and TB5, (see Fig. 3(b)) decrease the
air density and mass flow, so increasing the turbo lag, a slower response to engine speed changes [48e50].

3.3. Exhaust emissions

In order to take account of the humidity effect on NO formation, a dimensionless correction factor “kh,D” was calculated as [51]:

kh;D ¼ 1=½1
0:0182  ðHa
10:71Þ þ 0:045  ðTa
298Þ (4)

where Ha and Ta are humidity of the intake air (g H2O/kg dry air) and temperature of the intake air (K), respectively. HT-785 with an accuracy
of ±3 RH% and ±1  C was used for measured humidity and temperature of the intake air. The concentration values of NO, CO and HC
emissions were converted into mass values using Eq. (5)e(7), respectively;

NOmass ¼ 0:001587  ½NOwet  kh;D  GEXHW (5)

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
8 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12

Fig. 3. Variation of BTE (a) and exhaust gas temperature (b) as a function of engine speed.

COmass ¼ 0:000966  ½COwet  GEXHW (6)

HC mass ¼ 0:000479  ½HCwet  GEXHW (7)

where NOmass, COmass and HCmass are the corrected emissions concentration (g/h), [NO]wet, [CO]wet and [HC]wet are emissions concentration
on a wet basis (ppm) and GExHW are the exhaust gas average molecular weights (g/h) [51,52].
The exhaust emission test results expressed on a brake specific (g/kWh) basis for each experiment studied following sub-sections.

3.3.1. NO and NO2 emissions

Nitric oxide (NO) (90 vol.%), nitrogen dioxide (NO2) (5 vol.%), and nitruc oxide (N2O, N2O3 and N2O5) (5 vol.%) are constituents of NOx [10].
Chemical equilibrium considerations indicate that for burned gas at typical flame temperatures, each of N2O, N2O3 and N2O5 emissions is
very low even close to zero [48]. For this reason, N2O, N2O3 and N2O5 emissions were not considered in the present study. NO and NO2
emissions are shown for the test fuels in Fig. 4(a) and (b), respectively.
Thermal NOx, which is the main contributor, fuel NOx, and prompt NOx are contributors to the overall formation of NOx. High tem-
peratures and high oxygen concentrations result in high NO formation rates [53].
There are more molecules of oxygen in the chemical chains of n-butanol (21.58 wt.%) than cotton oil (11.2 wt.%) [2,16,22,26,54]. The
presence of high oxygen content in the combustion chamber affects rate of combustion temperature, as well as NO formation. With n-
butanol and cotton oil addition to diesel fuel, NO formations increased due to decrease CN of the blends (Fig. 4(a) and (b)). This increase is
very noticeable in the case of the test engine fueled with TB 3e5, because their CN significantly decrease (see Table 3) with the percentage of

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12 9

Fig. 4. Variation of NO (a) and NO2 (b) emission as a function of engine speed.

n-butanol and cotton oil being higher in the ternary blends. Further increasing of NO formations of ternary blends indicates that there is a
strong correlation between the physical and chemical properties such as latent heat of vaporization, lower heating value, CN, viscosity and
density, and thermal characteristics of the fuels [21]. Because the CNs of ternary blends are lower than diesel fuel, the injection period for
ternary blends would be longer during the ignition delay period. The longer ignition delay, the more fuel is burned abruptly during pre-
mixed combustion, and this causes an elevation of the pressures and temperatures during diffusion combustion that in turn affect NOx
emissions.
When compared to TB4 and TB5 which possess the same concentration of n-butanol (60 vol.%), increasing cotton oil ratio in ternary
blends resulted in production of more NO formation. TB5 has lower CN (29.7) which its property leads to longer ignition delay. The reason is
that longer ignition delay results in more homogeneous mixture formation. For TB5, lower in-cylinder temperature reaction occurs before
combustion than for TB1. As stated above, it indicates close interrelation between CN and NO formation. Same observations were found in
Refs [3,54].
Minimum NO emission values were measured as 2.08 g/kWh for diesel fuel at 1800 rpm and 2.63 g/kWh for TB2 at 4200 rpm. Maximum
NO emission values were obtained as 2.58 g/kWh for diesel fuel and 5.12 g/kWh for TB2 at 3000 rpm.

3.3.2. CO emission
Fig. 5(a) shows the variations of CO emissions of diesel fuel and ternary blends with respect to various engine speeds. As noticed from
Fig. 5(a), increasing presence of n-butanol in ternary blends compared to that of cotton oil has a decreasing effect on the formation of CO
emission. The lower density of n-butanol than diesel fuel causes easier evaporation in-cylinder; thus, the spray penetration length becomes
shorter. This effect boosts the mixing process, and supports to reduce CO emissions [16,27]. The maximum reduction of CO emission was
measured at 1800 rpm for TB4 as 80.7% compared to that of diesel fuel. The minimum CO emissions of 0.52 g/kWh was observed with TB4,
whereas the corresponding value with diesel fuel was found to be 1.25 g/kWh at the engine speed of 2600 rpm. In addition, TB4 and TB5,
which have maximum presence of n-butanol ratio (60%) in ternary blends, decreased CO emissions by an average of 32.69% and 21.59%,

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
10 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12

Fig. 5. Variation of CO (a) and HC (b) emission as a function of engine speed.

respectively, compared to that of diesel fuel. Ternary blends with higher ratio of n-butanol contents (TB4 and TB5) improve the fuel air
mixing process, especially in the fuel rich region of the combustion chamber by providing more oxygen, and mixing n-butanol with diesel
fuel leads to a leaning effect on the ternary blends because of lower stoichiometric air/fuel ratio of the n-butanol (see Table 3), thus lowering
CO emissions. However, increasing presence of cotton oil in ternary blends has an increasing effect on CO formations. Because of higher
density and viscosity of cotton oil (see Table 3), complete combustion process was significantly deteriorated for ternary blends with higher
percentage ratio of cotton oil (TB2 and TB3) [50]. Similar affects were observed for formation of HC emissions in Fig. 5(b).
Fig. 5(a) indicated that CO emissions for all test fuels favorably decreased at medium engine speeds between maximum torque
(2200 rpm) and power (3800 rpm), and then increased with decrease in the engine speed.

3.3.3. HC emission
The variations of HC emissions of diesel fuel and ternary blends with respect to engine speeds are shown in Fig. 5(b). It is indicated that
the test engine emitted more HC emissions at lower engine speeds. Air swirling velocity is very slow at lower engine speed, which causes
long ignition delay. Slow mixing of ternary blends with air results in an overrich mixture or quenching of the combustion reaction, and this
can result in incomplete combustion products and higher HC being present in the exhaust gases [48].
It is evident from Fig. 5(b), an increasing presence of n-butanol in ternary blends has a considerably decreasing effect on formation of HC
emissions. The maximum decrease of the average HC emission values were obtained by TB4 and TB5 compared to that of diesel fuel. This is
expected because of a greater amount of oxygen molecules participating in the combustion process for more complete combustion of TB4
and TB5, resulting in lower HC emissions. However, increasing presence of cotton oil in ternary blends has a reverse effect on HC emissions
especially in lower engine speeds because of its higher fuel density and viscosity. The higher density and viscosity seriously deteriorate into
fuel atomization and combustion in the combustion chamber [55]. Droplet diameter of the fuel spray plays a key role in heat-up, evapo-
ration, and combustion in the combustion chamber [56]. Increasing droplet diameter leads to a decrease in evaporation rate and increase in

Please cite this article in press as: A. Atmanlı, et al., Effects of higher ratios of n-butanol addition to dieselevegetable oil blends on performance
and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008
 A. Atmanlı et al. / Journal of the Energy Institute xxx (2014) 1e12 11

ignition delay as well as HC formation. As shown in Fig. 5(b), TB3 and TB4, which have maximum presence of cotton oil ratio of 30% in
ternary blends, exhibit the opposite effect on HC emissions compared to other ternary blends.

4. Conclusions

In the present study, five different diesel fuelecotton oilen-butanol ternary blends were selected in the soluble area of the ternary phase
diagram for low temperature (
15  C) operability. Also, the effect of component concentrations on phase behavior of ternary blends was
studied. The effects of basic fuel properties of ternary blends on engine performance and exhaust emissions were discussed in detailed. The
main conclusions derived from present investigation are summarized below:

 All ternary blends evaluated in this study can be effectively used at
15  C system temperature without any phase separation.
 Increasing presence of n-butanol in the blends improved density, kinematic viscosity and CFPP, while deteriorated CN and heating value
of the ternary blends.
 Similar trend of n-butanol was observed with cotton oil concerning the CN and heating value of the ternary blends.
 The average brake torque, brake power, BTE and exhaust gas temperature values of ternary blends decreased by increasing presence of
n-butanol in the blends compared to those of diesel fuel.
 Compared to presence of n-butanol in the ternary blends, the addition of cotton oil to ternary blends had increasing effect on the brake
torque, brake power, BTE and exhaust gas temperature due to its high heating value and low latent heat of vaporization compared with
that of n-butanol.
 Increasing presence of n-butanol and cotton oil in ternary blends has an increasing effect on BSFC. BSFC increasing effect is found to be
very obvious with increasing n-butanol concentration when compared to that of cotton oil.
 Addition of n-butanol and cotton oil to diesel fuel leads to increased NO and NO2 formations. Increasing presence of n-butanol in ternary
blends compared to that of cotton oil has drastically decreasing effect on formation of CO and HC emissions.
 TB4 and TB5 can be used as alternative fuels in a diesel engine for decreasing CO and HC emissions at the expense of deteriorating BSFC
and BTE.
 Presence of higher n-butanol concentrations in TB 3-5 have a decreasing effect on those of CNs. This problem can be solved by adding
cetane-enhancing additives such as 2-ethylhexylnitrate.

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and exhaust emissions of a diesel engine, Journal of the Energy Institute (2014), http://dx.doi.org/10.1016/j.joei.2014.09.008