Fuel 117 (2014) 450457

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Effect of the degree of unsaturation of biodiesel fuels on the exhaust emissions of a diesel power generator
S ehmus Altun
Department of Mechanical Education, Technical Education Faculty, Batman University, 72060 Batman, Turkey

h i g h l i g h t s
 The effect of the degree of unsaturation of biodiesels on diesel emissions was investigated.  Biodiesels resulted in smoke opacity, with an increase in BSFC compared to ULSD.  Saturated biodiesel had highest cetane number and lowest adiabatic ame temperature which was good to reduce NOx emission.  The cetane number and adiabatic ame temperature appear to be the key properties that determined the emissions.

a r t i c l e

i n f o

a b s t r a c t
In this work, three biodiesel fuels with iodine numbers ranging from 59 to 185 were tested in a directinjection diesel engine powered generator set at constant speed of 1500 rpm under variable load conditions to investigate the effect of the degree of unsaturation of biodiesel fuels, which are quantied by the iodine number, on the performance and exhaust emissions of a diesel engine. The increase in unsaturation involved a decrease in cetane number, and therefore, allowed for the maximization of the effect of the cetane number, while other properties, such as oxygen content, heating value, and viscosity, varied within a small range. Experimental results showed that biodiesel fuels resulted in lower emissions of nitrogen oxides, carbon monoxide, and smoke opacity, with some increase in emissions of unburned hydrocarbons. With their low energy content, neat biodiesel fuels resulted in an increase in fuel consumption compared to the conventional diesel fuel (ultra-low sulphur diesel). The degree of unsaturation of biodiesel fuels had effects on engine emissions via its effect on the cetane number and adiabatic ame temperature while engine performance was not signicantly affected by the type of biodiesel fuel or its degree of unsaturation. The biodiesel having lowest iodine number had highest cetane number, and lowest density and adiabatic ame temperature, which was good to reduce NOx emissions, as it agreed with experimental results. Additionally, more unsaturated biodiesel fuels showed higher NOx emissions, smoke opacity, and lower HC emissions. It can be said that cetane number and adiabatic ame temperature are responsible for such results. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 1 August 2013 Received in revised form 6 September 2013 Accepted 10 September 2013 Available online 25 September 2013 Keywords: Biodiesel Iodine number Degree of unsaturation Diesel emissions

1. Introduction As a consequence of the increasing concern about environmental pollution and more stringent regulations on exhaust emissions, reduction in engine emissions have become a major subject in engine studies. In addition, much effort has been made to reduce dependence on the petroleum as it is obtained from limited re-

serves. These concerns have led to much research on alternative renewable fuels in the last decade. Among the proposed alternative fuels, biodiesel has received much attention for using in diesel engines in recent years [1,2]. Biodiesel is typically produced by transesterication reaction of vegetable oils or animal fats with methanol in the presence of a catalyst to yield glycerin and methyl esters, and it can be used directly or blended with fossil diesel fuels

Abbreviations: ASTM, American Society for Testing and Materials; US EPA, United States Environment Protect Agency; GC, gas chromatograph; FID, ame ionization detector; LHV, lower heating value (kJ/kg); ppm, parts per million; rpm, revolution per minute; CO, carbon monoxide; HC, hydrocarbons; NOx, nitrogen oxides; BSFC, brake specic fuel consumption (g/kW h); BTE, brake thermal efciency (%); IN, iodine number (g of I2/100 g); ULSD, ultra-low sulphur diesel; POME, palm oil methyl ester; CSOME, cottonseed oil methyl ester; WFOME, waste sh oil methyl ester. Tel.: +90 488 2173675; fax: +90 488 2157201. E-mail address: saltun72@yahoo.com 0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.09.028

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in diesel engines with no or little modications. However, some diesel engine manufacturers do not allow using neat biodiesel or its blends instead of fossil diesel fuels. Warranties are often applied to only biodiesel that fullls the ASTM D 6751-03 for USA and EN 14214 for European Union standards [3,4], and in Europe in concentrations below 7%, as specied by standard EN-590. Although the fuel properties of biodiesel can vary with production technologies and feedstock, it has some fuel advantages over fossil diesel fuel, including renewability, biodegradability, better lubricity, and high ash point and oxygen content [5]. Lapuerta et al. [6] concluded in their review study that using biodiesel fuels in diesel engines result in reductions in CO, HC and particulate emissions due to the higher oxygen content of biodiesel compared to fossil diesel fuel. However, in the case of nitrogen oxides (NOx), despite the highest consensus lies in an increase of NOx emissions with biodiesel, some contradictory trends have also been reported. Some of the researchers found increases in NOx emissions; some others did not nd any differences between diesel and biodiesel fuels, and others found decreases in NOx emissions while using biodiesel. This is mainly attributed to differences in physicochemical properties of biodiesel, its effect on injection timing, ignition delay, adiabatic ame temperature, radiative heat loss, and other combustion phenomena, also varies with engine technology and operating conditions [7,8]. However, several researchers indicate that NOx formation in biodieselfueled diesel engines is highly dependent on the degree of unsaturation and cetane number of biodiesel [9,10]. In general, higher degrees of saturation correlate with higher cetane numbers, and saturated biodiesel fuels (i.e. without double bonds) produce lower amounts of NOx than unsaturated fuels [11]. In a study done by US EPA (United States Environment Protect Agency) [12], it was conrmed the direct relationship between NOx emissions and molecular unsaturation. It was observed in the study that on average, biodiesel obtained from soybean oil provided a 15% increase in NOx emissions as compared to those with fossil diesel fuel, rapeseed oil based biodiesel provided a 12% increase, while biodiesel produced from animal fats led to only a 3% increase. The study of Wyatt et al. [13] also showed that the animal fat-based biodiesel fuels, which are highly saturated, had lower NOx emission levels than did the soybean oil based biodiesel fuel (unsaturation ones). In the same way, Wang et al. [14] found a measurable reduction in NOx emissions with biodiesel obtained from high oleic soybean oil compared to normal soybean oil based biodiesel which contains 25% oleic acid in its fatty acid composition. In another study by Ng et al. [15], NO emission was found to decrease with increasing palm and coconut oil biodiesels content in the fuel when compared with fossil diesel, opposite to the emissions of the highly unsaturated ones (soybean oil based biodiesel), where NO level are higher in relation to that of fossil diesel.

However, the effect of the degree of unsaturation of biodiesel on opacity and particulate emissions is much less known. There is no consensus about whether or not the degree of unsaturation of biodiesel fuels affects smoke opacity and/or particulate emissions. Although a few authors found a slight dependency [16], there are also others who found no effect of the biodiesel feedstock on exhaust opacity and particulate emissions [17]. In this work, effect of the degree of unsaturation of biodiesel fuels, which are quantied by the iodine number, on the characteristics of the engine was investigated experimentally in a diesel engine powered generator set. Biodiesel fuels were produced from different feedstock such as palm oil, cottonseed oil and waste anchovy sh oil via transesterication process, and consequently their iodine values were different (from 59 to 185). The increase in unsaturation involved a decrease in cetane number, and therefore, allowed for the maximization of the effect of the cetane number, while other properties, such as oxygen content, heating value, and viscosity, varied within a small range.

2. Experimental section 2.1. Test fuel characterization A conventional diesel fuel (Ultra-Low Sulphur Diesel (ULSD)) was provided from Shell fueling station located in Batman, Turkey, and used as the reference fuel in this work. Biodiesel fuels were produced from different feedstock such as palm oil, cottonseed oil and waste anchovy sh oil through transesterication reaction using methanol in the presence of an alkali catalyst. Biodiesel fuels were selected to have different values of iodine number, from 59 to 185. Among the biodiesels tested, palm oil is the most saturated one, and consequently, it has a high cetane number and low density. Cottonseed oil is available abundantly in Turkey, and waste anchovy sh oil is also taken into account as a promising alternative feedstock for biodiesel production [18]. In addition to these, they have more unsaturated fatty acids than palm oil. For transesterication reaction, methanol and sodium hydroxide with purity of 98% were provided from Renery and Petro-Chemistry laboratory at Batman University, Batman, Turkey. After solving the NaOH catalyst in methanol at room temperature in a magnetic stirrer, the moisture-free oils were added to the reaction tank to start the transesterication reaction. The mixture was agitated throughout at 60 C. After glycerol separation, the ester phase was washed with warm distilled water. After washing process, the methyl ester was subjected to a heat at 110 C to remove excess alcohol and water, and then ltered. To determine the fatty acid prole, GC analyses were carried out on a Shimadzu GC2010 plus Gas

Table 1 Speciation of tested fuels. Fatty acid type Linoleic Palmitic Oleic Stearic Miristic Palmitoleic Trideconoic Linolenic Eicosatetraenoic Eicosapentaenoic Docosapentaenoic acid Docosahexaenoic Others Total unsaturated Carbon chain C18:2 C16:0 C18:1 C18:0 C14:0 C16:1 C13:0 C18:3 C20:4 C20:5 C22:5 C22:6 Palm oil 11.8155 39.7834 43.5639 3.1628 1.3810 0.2933 55 Cottonseed oil 57.1 20.9 17.9 2.43 0.65 0.46 0.29 0.18 75 Waste anchovy sh oil 4.43 20.20 19.71 4.2 6.71 6.59 1.64 0.79 10.41 0.82 21.58 1.53 69

452 Table 2 Fuel properties. Properties Chemical formula % C (wt.) % H (wt.) % O (wt.) IN (g of I2/100 g) MW (kg/kmol) Cetane number LHV (MJ/kg) Density (kg/m3) Kin. Viscosity (mm2/s) Flash point (C) CFPP (C) Stoichiometric air/ fuel ratio ULSD 86.5 13.5 0 0 212 51 42 835 2,8 55 15 Palm oil C18.10H34.89O2 76.40 12.36 11.24 59 284 68 37.23 876 4.763 165.2 +11 12.55 Cottonseed oil C18.49H34.77O2 76.85 11.98 11.07 115 289 56 37.25 884 4.33 180.6 +6 12.48

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Waste anchovy sh oil C19.07H33.87O2 77.59 11.57 10.84 185 295 52 37.30 892 4.435 182.4 +4 12.43

Some properties of biodiesel fuels studied here are shown in Table 2. Density, kinematic viscosity, ash point and CFPP were measured, whereas other properties were calculated or obtained from suppliers. Density and kinematic viscosity were measured at 15 C and 40 C, respectively. Carbon and Hydrogen values for ULSD was taken from Ref. [19] where these values were taken from Shell Global Solutions (UK). Cetane number, viscosity, heating value and density are the main physical properties of the fuel that affect the diesel combustion process. These properties are affected by the degree of unsaturation to different extents, as inferred from Table 2. For instance, the cetane number, which reects the ignition quality of the fuel, is higher in the case of POME (high saturated fuel) compared to cottonseed oil and waste anchovy sh oil. In this study, there was a good correlation between density and the degree of unsaturation. The biodiesels having highest density, in descending order, are: WFOME, CSOME, and POME. The lower heating values (LHV) of the saturated and unsaturated fuels varied within a narrow range. The kinematic viscosity of the test fuels slightly decreased with the degree of unsaturation.

Table 3 The specication of the engine. Model of engine Engine type Injection pump Number of cylinder and arrangement Bore stroke Compression ratio Rated speed Rated power Aftertreatment Generator details Power output Frequency Tension 1.4 diesel Inter heavy-duty Four strokes, direct injection, water-cooled and naturally aspirated Mechanically controlled in-line type 3-In line 80 mm 90 mm 22.5:1 1500 rpm 12.5 kW None 9.6 kW 50 Hz 230/400 V

2.2. Experimental equipment The experimental study was carried out in a three-cylinder, four-stroke, naturally aspired and direct-injection diesel engine powered generator, whose main characteristics are shown in Table 3. A bank of electric resistances was used to supply the load applied to the generator. Fig. 1 illustrates the schematic diagram of the experimental set-up. The generator is linked up directly to the engine from the ywheel of the engine to the clutch of the generator. The engine is tted with an in-line, three-cylinder fuel injection pump coupled to a variable-speed mechanical governor. Several temperatures such as engine oil, coolant and exhaust gas temperatures were measured to monitor and control the engine operation. Fuel consumption was determined by weighing fuel used for a period of time on an electronic scale with a precision of 0.1 g. Therefore, the engine was modied in order to have a fuel consumption control by gravity, changing the original fuel tank by a remote tank, which was placed on a balance. In each test, fuel consumption, opacity and exhaust gas emissions, such as nitrogen oxides (NOx), carbon monoxide (CO) and total unburned hydrocarbons (HC) were measured. In this study, gaseous emissions were measured by using a gas analyzer (Capelec Cap 3200) and the opacity level was monitored by means of Capelec smoke opacity tester. Measurement devices were calibrated, and their lines were cleaned before the experiments. The accuracy of the measurements and uncertainties in calculated results are shown in Table 4. The adiabatic ame temperature shows exclusively the inuence of the

Chromatograph equipped with a ame ionization detector (FID). The GC uses a 30 m 0.25 mm ID DB-23 capillary column (lm thickness of 0.25 lm). The fatty acid composition is given in Table 1. Palm oil biodiesel (denoted as POME) is dened by having a balance between saturated (39.7% C16:0) and monounsaturated (43.5% C18:1) methyl esters while cottonseed oil biodiesel (denoted as CSOME) is predominantly unsaturated (75%), having signicant contents of diunsaturated (17.9% C18:2) and especially triunsaturated (57.1% C18:3) methyl esters. On the other hand, waste anchovy sh oil (denoted as WFOME) is also predominantly unsaturated (69%) and it has more polyunsaturated methyl esters.

Control panel

Load bank

Gas emissions analyzer

Opacity meter

Generator

3 cylinders DI diesel engine

Exhaust out

To atmosphere

Fuel reservoir Electronic scale

Air Fuel Air filter Air

Fig. 1. Schematic diagram of the experimental set up.

S . Altun / Fuel 117 (2014) 450457 Table 4 The accuracy of the measurements and the uncertainties in the calculated results. Parameter Load Speed Time Temperatures HC CO2 CO O2 NOx Smoke Calculated results BSFC BTE Accuracy 1% 15 rpm 0.1s 1% 1 ppm 0.1% 0.001% 0.01% 1 ppm 0.1% Uncertainty 2.5% max. 2.5% max.

453

engines, diesel engine powered generators operate under different load and constant speed conditions; that is why such operating conditions were selected for the tests in this study. Since the gas mixture in the engine cylinder has a longer residence time with high combustion temperatures under low speed and high load conditions, it is expected that the effect of biodiesel on NOx emissions will be more signicant under these conditions; hence, it is also of interest to investigate the effect of biodiesel on NOx emissions under such conditions [21]. Therefore, NOx emissions vs. the degree of unsaturation were evaluated under low speed and high load conditions. This test condition yielded the minimum air/fuel ratio and maximum smoke opacity among the collection of tested steady operation conditions. 3. Results and discussion

molecular structure of the fuel on NOx emission, regardless of other thermodynamical conditions which may change in combustion chamber. For the calculation of the adiabatic ame temperature, a chemical equilibrium model [20] which takes 29 chemical species into consideration was used. The initial conditions of 80 bar and 900 K were selected as representative of the conditions reached around the top dead center in the combustion chamber of a diesel engine. The constant-pressure condition (which permitted to calculate the adiabatic temperature from enthalpy balance) was preferred to the constant-volume condition (associated to internal energy) consistently with the local (rather than bulk) character of the NO formation mechanisms. 2.3. Test conditions The test engine was run with a preliminary investigation of the engine running on a diesel reference fuel (ULSD), and then the same procedure was repeated for other test fuels by keeping the same operating conditions. Except for the reference fuel, three biodiesel fuels, i.e. POME, CSOME and WFOME were also tested. Additionally, a blend of reference fuel with biodiesel fuels in percentage of 20% by volume (denoted as POME_20, CSOME_20 and WFOME_20) were tested, too. The engine was considered to be at steady state when the exhaust temperature reached a constant temperature. Before starting a new experiment, the lines of the measurement equipments were cleaned to remove residues of the previous test. A hand pump was used to drain fuel in between fuel changes. After that, the engine was warmed with the new fuel for at least 30 min to cleanup any remains of the previously used fuel from the fuel system. No modication on the engine or fuel injection system was applied, and test engine had no aftertreatment system. The tests are performed using each of the conventional and alternative fuels with the engine working at a speed of 1500 rpm and at different loads. Different from automotive diesel
1000
ULSD POME CSOME WFOME

Experimental results obtained for brake specic fuel consumption, brake thermal efciency, HC, CO, NOx emissions and smoke opacity are presented in this section. Results obtained for tested fuels as a function of load are shown in rst gures, and then data were reorganized and presented in two different gures to study the effect of the biodiesel content and its degree of unsaturation. 3.1. Engine performance A decreasing trend in brake specic fuel consumption (BSFC) was observed when increasing the load for all tested fuels, as shown in Fig. 2. This is mainly due to lesser contribution of the mechanical losses to the total power output at high load conditions. At higher loads, the conversion of heat energy to mechanical work increases with the rise in combustion temperature that leads to a decrease in BSFC with respect to the load [22]. In the same gure, it can be seen that there is an increase in BSFC values of pure biodiesel fuels in comparison with ULSD, and the increase is almost proportional to the differences in lower heating value of the fuels. In the case of blended fuels containing 20% biodiesel, BSFC was in between those of their components corresponding to the blending proportions [23]. The reason for higher BSFC with biodiesel fuels is evidently because of their lower heating value when reference diesel fuel and biodiesel fuels with signicant differences in heating value are compared. To maintain the same power output at equal speed, more biodiesel has to be injected into combustion chamber due to its low energy content compared with fossil diesel [23]. When brake thermal efciency is examined, it will be clearly seen that the efciency of ULSD, biodiesel fuels and intermediate blends are very similar as can be observed in Fig. 4 since brake thermal efciency is a function of BSFC and LHV of the fuel for a constant power output. BSFC values for tested fuels were reorganized in Fig. 3 to further study the effect of the biodiesel content (Fig. 3a)
1000

800

800 BSFC (g/kWh)

BSFC (g/kWh)

ULSD POME_20 CSOME_20 WFOME_20

600

600

400

400

200 0 2 4 6 Power output (kW) 8

200 0 2 4 6 Power output (kW) 8

Fig. 2. Break specic fuel consumption.

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12

14

(BSFC/BSFC ULSD _1) . 100 (%)

(BSFC/BSFC ULSD _1).100 (%)

POME CSOME WFOME

12 10 8 6

(a)
0 0 20 40 60 80 100 Biodiesel content in fuel (%v/v)

(b)
4 40 60 80 100 120 140 160 180 200 IN (g of I 2 /100g) for pure biodiesel fuels

Fig. 3. Increase of BSFC for blends (a) and for pure biodiesel fuels (b).

25 20 15 10 5 0 0 2 4 6 Power output (kW) 8

ULSD POME CSOME WFOME

25 20

BTE (%)

15 10 5 0 0 2

ULSD POME_20 CSOME_20 WFOME_20

BTE (%)

4 6 Power output (kW)

Fig. 4. Brake thermal efciency.

and it was calculated as the average of the seven operation modes tested for that fuel, and the effect of iodine number of pure biodiesel was also shown in Fig. 3b. It was found that the increase in BSFC was linear with the biodiesel content in the fuel blend, up to about 11% in the case of WFOME, very close to the difference of heating values between ULSD and biodiesel fuels, as shown in Table 2. The biodiesels that result in the highest fuel consumption, in descending order, are these: WFOME, CSOME, and POME; and thus it can be said that BSFC slightly increased with increasing degree of unsaturation characterized by iodine number (IN) as shown in Fig. 3b. Differences in brake thermal efciency (BTE) between pure or blended biodiesel fuels and ULSD are shown in Fig. 4, and it shows similar BTE values except for higher loads where ULSD has

slightly low efciency. Moreover, it can be seen in Fig. 5a that there is no linear change in BTE with biodiesel content, and also in Fig. 5b where BTE slightly decreased by increasing the degree of unsaturation. The results indicated that the performance was not signicantly affected by the type of biodiesel fuel or its degree of unsaturation, and thus this allows for an expressive analysis of the effect of the degree of unsaturation of biodiesel fuels on exhaust emissions. 3.2. Gaseous emissions Fig. 6 shows the total unburned hydrocarbons (HC) emissions for ULSD and the biodiesel fuels of various origins. Biodiesel fuels

7
POME

(BTE/BTE ULSD-1) . 100 (%)

5 3 1 -1

WFOME

(BTE/BTE ULSD-1).100 (%)

CSOME

6 5 4 3 2 1 0

(a)
-3 0 20 40 60 80 Biodiesel content in fuel (%v/v) 100

(b)
40 60 80 100 120 140 160 180 200 IN (g of I 2 /100g) for pure biodiesel fuels

Fig. 5. Difference of BTE and for blends (a) and for pure biodiesel fuels (b).

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455

200

HC Emissions (ppm)

150

HC Emissions (ppm)

ULSD POME CSOME WFOME

200

150

ULSD POME_20 CSOME_20 WFOME_20

100

100

50

50

0 0 2 4 6 Power output (kW) 8

0 0 2 4 6 Power output (kW) 8

Fig. 6. Unburned hydrocarbon emissions.

100

(HC/HCULSD -1) . 100 (%)

75

(HC/HCULSD -1).100 (%)

POME CSOME WFOME

90

80

50

70

25

60

(a)
0 0 20 40 60 80 100 Biodiesel content in fuel (%v/v)

(b)
50 40 60 80 100 120 140 160 180 200 IN (g of I2 /100g) for pure biodiesel fuels

Fig. 7. Difference of HC emissions and for blends (a) and for pure biodiesel fuels (b).

tested result in higher HC emissions than ULSD. This is an unexpected result as HC emissions are usually found to signicantly decrease with biodiesel. The observed increases in HC emissions could probably be associated with excessive viscosity and low volatility of pure biodiesel fuels, which lead to problems in fuel atomization and evaporation, as compared with ULSD, in the case that test engine is a low-injection-pressure one. Jindal et al. [24] also reported that HC emissions tend to increase with increase in compression ratio and also on reduction in injection pressure. On the other hand, a decrease in HC emissions was observed as the degree of unsaturation of the biodiesel fuels increased, as shown in Fig. 7. This result is in agreement with the ndings by Karavalakis et al. [25] who obtained lower THC emissions when the degree of unsaturation of the biodiesel fuel was increased. It was reported in their study that the lower volatility of the saturated blends may lead to incomplete vaporization and combustion of the fuel, thereby increasing HC emissions. Exhaust CO emissions for all tested fuels were very small in the range, and there appeared a slight increase with the increase in load, so they were not plotted in any Figure. However, the palm-based biodiesel produced the lowest CO emissions among the biodiesels tested. The difference in CO emission with different biodiesels is likely to be a combined effect of oxygen content and cetane number as the composition of the palm-based biodiesel, which corresponds to a high cetane number due to its higher content of linear hydrocarbons. This result seems to agree with a study conducted by Wu et al. [26], indicating that CO emissions decrease as the saturation level is increased. The NOx emissions for ULSD and the biodiesel fuels of various origins are plotted in Fig. 8 for high load conditions, where they yielded the minimum air/fuel ratio and maximum smoke opacity among the collection of steady operation conditions. Results pre-

sented in Fig. 8 show that the use of biodiesel fuels leads to a slight decrease in NOx emissions, especially in the case of highly saturated biodiesel as a consequence of their higher cetane number, opposite to trends generally observed (see Table 2). NOx-decreasing trend when using more saturated biodiesel fuels has also been reported in other works [27,28]. The reduction of aromatic content in the fuel also contributes to decrease NOx emissions, as reported by Kalligeros et al. [29]. Several researchers indicated that there is a strong relationship between iodine number, which is a good indicator for the degree of unsaturation, and NOx emissions [3032]. This effect can also be more easily observed in Fig. 9. As the iodine value of POME is lower than those of CSOME and WFOME, and hence decrease in NOx emissions is expected. The differences in
1200 ULSD POME20 1100 CSOME20 WFOME20 1000 POME CSOME WFOME

NOx Emissions (ppm)

900

800

700

600
Fig. 8. NOx emissions for fuels tested.

456

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(NOx /NOxULSD-1) . 100 (%)

-2 -4 -6 -8 -10 -12 -14 -16 0 20 40 60

(NOx/NOx ULSD -1).100 (%)

POME CSOME WFOME

-10

-12

-14

(a)
80 100

(b)
-16 40 60 80 100 120 140 160 180 200

Biodiesel content in fuel (%v/v)

IN (g of I2 /100g) for pure biodiesel fuels

Fig. 9. Difference of NOx emissions and for blends (a) and for pure biodiesel fuels (b).

Adiabatic flame temperature (K)

2760 2740 2720 2700 2680 2660 2640 2620 0.9 0.95 1 1.05 1.1 1.15 1.2
POME CSOME WFOME

Relative fuel/air ratio

Fig. 10. Adiabatic ame temperature at constant pressure of the tested fuels for typical initial conditions.

the adiabatic ame temperature, which is shown in Fig. 10, could be pointed out to explain the observed reduction. The adiabatic ame temperature was calculated from a 29 species equilibrium model, which is presented in detail in experimental equipment section, for a wide range of local relative fuel/air ratios and for typical initial conditions indications. Fig. 10 shows that the adiabatic ame temperature increases slightly as the degree of unsaturation increases and reaches maximum levels around equivalence ratios of 1.065 in all cases. POME is the most saturated one (lowest IN) and it has lowest adiabatic ame temperature, which is good to reduce NOx emissions. In the opposite, WFOME is most unsaturated (IN = 185), and it has highest adiabatic ame temperature. Knothe et al. [33] also pointed out that the adiabatic ame temperature was responsible for a reduction in NOx emissions for the saturated esters.

80

ULSD POME20 CSOME20 WFOME20

POME CSOME WFOME

3.3. Smoke opacity Smoke opacity level is a measure of the relative amount of light extinction of a light beam inciting perpendicularly to the exhaust gas stream, and is an indicator of soot emissions in the exhaust. It was observed that increasing contents of biodiesel in the fuel decreased the opacity of the exhaust gas, and it increased with increase in load for all tested fuels, as shown in Fig. 11. This is because of the oxygen content of biodiesel fuels increases the oxygen present in fuel rich regions of the combusting fuel spray, reducing the amount of soot formed [34]. The reduction of aromatic compounds in the fuel and the lower stoichiometric need of air can be given as other reasons. Fig. 12a shows that, smoke opacity decreased consistently with the decrease in aromatic compounds and the increase in oxygen content in the fuel blends. The
POME CSOME WFOME

Smoke opacity (%)

60

40

20

0
Fig. 11. Smoke opacity for fuels tested.

-20

(Smoke/Smoke ULSD -1) . 100 (%)

-5 -10 -15 -20 -25 -30 -35 0

(Smoke/Smoke ULSD-1).100 (%)

-25

-30

(a)
20 40 60 80 Biodiesel content in fuel (%v/v) 100

(b)
-35 40 60 80 100 120 140 160 180 200 IN (g of I 2 /100g) for pure biodiesel fuels

Fig. 12. Difference of opacity for blends (a) and for pure biodiesel fuels (b).

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effect of the iodine number of the biodiesel fuel in the smoke opacity can be observed from Fig. 12b. As the iodine number was increased, increase in opacity was found, and then it decreased. Unsaturated functional groups contribute to increased sooting tendency, as reported by Barrientos et al. [35], other researchers have also found decreases in PM emissions and smoke opacity with increased unsaturation [16]. However, biodiesel fuels showing high exhaust temperature (such as those with highest IN) continued such trend by promoting soot oxidation. On the other hand, Graboski et al. [36] did not found any correlation either with the chain length or with the unsaturation level. They argued that PM emissions depend on the oxygen content, which is almost constant for every biodiesel or pure ester. However, there was some dependence on the density and cetane number. When the biodiesel density was higher than 895 kg/m3 or the cetane number lower than 45 the PM emissions increased considerably [36]. Choi et al. [37] also concluded that the effect of the composition and structure on PM emissions is negligible as compared to the oxygen content, which was acknowledged as the main factor causing PM emission reductions. 4. Conclusions From the experimental work carried out to investigate the effect of the degree of unsaturation of biodiesel fuels on engine characteristics, the following conclusions can be drawn. In comparison with ULSD, biodiesel fuels showed higher BSFC throughout all the power range investigated, and similar BTE values. Biodiesel fuels reduced emissions of oxides of nitrogen and carbon monoxide, and smoke opacity, with the magnitude of these decreases depending upon the biodiesel fuel origin. HC emissions were higher when the biodiesel fuels were used instead of ULSD, with types of biodiesel producing similar results. Results obtained showed that there was no signicant effect of the degree of unsaturation on the engine performance while the effect on emissions was clear. More unsaturated biodiesel fuels showed higher NOx emissions, and lower HC emissions. Although increasing contents of biodiesel in the fuel decreased the opacity of the exhaust gas, there was not found a linear changing with degree of unsaturation. According to the experimental results obtained in this work, the cetane number and adiabatic ame temperature appear to be the key properties that determined the exhaust emissions of the biodiesel fuels. Acknowledgements This work was partially supported by the Unit of Scientic Research Projects of Batman University, Turkey with Research Project No. BAP-2010-MF-01. I am thankful to Prof. Dr. Magn Lapuerta from University of Castilla La-Mancha, Ciudad Real, Spain for his valuable contribution and advices, and also the Council of Higher Education of Turkey (YK) for supporting the authors stay at the University of Castilla La-Mancha. References
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