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Lin and Wang [17] conducted a research on failures. Carboxylic acids and their derivatives
effects of an oxygenated additive on the (esters and amides) are mostly suggested
emulsification characteristics of two- and three- additives due to their wear resisting (preventing)
phase diesel emulsions. The results specifications [23]. EDTA is only reactive with
demonstrated that the viscosities of oil-in-water metal ions in solution, so it is not reactive with
(O/W) and water-in-oil (W/O) two-phase fuel injection system (fuel pump, fuel rails,
emulsions increase with the increase of their injectors, gaskets, pistons, cylinder heads, etc.)
inner phase content and the addition of an materials which are in compound forms.
oxygenated agent. The addition of diglyme Thereby, positive effects of EDTA on
agent to the emulsions deteriorates the combustion were utilized without forming any
emulsification activity (EA) and emulsification damage on fuel injection system. Chemical
stability (ES) of W/O and oil-in-water-in-oil structure of EDTA is depicted in Figure 1.
(O/W/O). Zakharckhuk and Tkachuk [18] put
forward a new technology on production and
performance properties of isopropyl ester of
rapeseed oil and they concluded that the
synthesized biofuel was of a high quality and
can be used in diesel engines.
On the other hand, effects of variation of
compression ratio especially in diesel engines
have also attracted great interest of researchers.
Muralidharan and Vasudevan [19] studied on
the influence of CR on the performance of a
VCR engine running with waste cooking oil and Figure 1. Chemical structure of EDTA
its diesel blends fueled VCR engine to
determine effects of CR variation on
performance and they concluded that B40 blend
depicted better performance in comparison to
standard diesel at CR 21. Hirkude and Padalkar
[20] made an investigation on the relationship
between BSFC and exhaust gas temperature
(EGT) with the increase of CR for waste fried
oil methyl ester blend operated diesel engine.
Bora and Saha [21] conducted an experimental
analysis on influence of CR variation on Figure 2. Biodiesel production process
performance and emissions of rice bran 2. Experimental Techniques and
biodiesel-biogas dual fueled VCR diesel engine Specifications
under 3 different CRs. They concluded that, in 2.1. Trans-esterification process
general, increment of CR drastically effects
Sunflower biodiesel (B100) was produced by
performance and emission characteristics.
trans-esterification of sunflower oil with 20%
In this study, due to its substantial high
(by vol.) methanol in the presence of ratio of
hydrogen and oxygen contents, EDTA was
5/1000 (by wt.) NaOH catalyst. In the first step,
chosen as additive for sunflower methyl ester
waste sunflower oil underwent FFA reduction
(B100). The classic structural formula of EDTA
process (under 1%) to enhance its biodiesel
is C10H16N2O8. EDTA is synthesized from
conversion efficiency. Then, the oil was heated
ethylene diamine, formaldehyde and a source of
up to 60-65ºC on a heater and methanol-NaOH
cyanide (HCN or NaCN). EDTA is a novel
solution was poured into it to conduct trans-
molecule for complexion of metal ions. It is
esterification reaction at about 60ºC for 1 hour
polyprotic acid containing four carboxylic acid
on condition that methanol was condensed
and two amine groups with lone pair electrons
during the reaction by a cooling tower. After the
[22]. Wear resistive additives place a high
reaction, the sample was taken into a separation
priority for fuels to prevent rapid engine
International Journal of Automotive Engineering and Technologies, IJAET 8 (3) 140-149 143
flask for separation of glycerin from the oxygen and hydrogen contents) as well as
biodiesel. Subsequently, the washing and drying considering the cost. EDTA depicted very small
(at about 105ºC) processes of biodiesel were corrosion activity (negligible) with metals and
carried out and the neat biodiesel was achieved. alloys due to its chemical structure. In order to
Production steps of biodiesel and schematic of observe solubility, EDTA was added into B100
trans-esterification reaction are exhibited in by weight ratios of 0.002%, 0.005%, 0.010%,
Figure 2 and Figure 3, respectively. 0.015%, 0.017%, 0.019% and 0.020%. The
blends were mixed with an ultrasonic mixer and
kept under room temperature for 3 weeks. It was
concluded that, above ratio of 0.015% (by wt.),
EDTA showed insolubility.
2.3. Fuel properties determination procedure
The devices used to determine the fuel
Figure 3. Demonstration of trans-esterification reaction properties are shown in Table 1.
Cetane Number (CN), an important parameter
2.2. Selection of EDTA as biodiesel additive for biodiesel quality, is a dimensionless
Investigations were made on several features of indicator related to the ignition characteristics of
chemicals to select an appropriate additive for a fuel in a cylinder, and can impact the engine’s
B100 viz. reaction activity with metal and alloys startability, noise level, and exhaust emissions.
(reactivity with fuel injection system material), Better combustion achieved as a result of less
miscibility in B100 ambient, chemical content ignition delay time or higher cetane number [24,
for suitability as a fuel additive (specially 25].
Table 1. Fuel properties and measurement devices
Property Device Accuracy Measuring Range
Cetane Number Zeltex ZX440 3% -
Lower Heating Value (LHV) IKA-Werke C2000 Bomb Calorimeter 0.001 K -
±0.001
Density Kyoto Electronics DA-130 -
g/cm3
Viscosity Saybolt Universal Viscosimeter - Ambient temp. to 240 oC
Tanaka Automated Pensky-Martens
Flash Point - Ambient temp. to 370 oC
Closed Cup Flash Point Tester APM-7
+51 oC to – 40 oC with
tap water of 20 oC and
Pour Point Tanaka MPC-102 -
+51 oC to – 65 oC with
cooling liquid of -35 oC.
Density, viscosity, cold-flow properties, lower will ignite, liquids with lower FP can be ignited
heating value (LHV), flash point compose other easier [33]. The quantity known as lower
measurements of fuel quality in diesel engines. heating value (LHV) (net calorific value (NCV)
Viscosity, a measure of resistance to flow of a or lower calorific value (LCV)) is determined by
liquid due to the internal fluid friction [26] and subtracting the heat of vaporization of the water
is an important property because of its direct vapor from the higher heating value. This treats
relation with the fuel injection process in any H2O formed as a vapor. The energy required
engines [27, 28]. Biodiesel viscosity is usually to vaporize the water therefore is not released as
higher than that of diesel, which results in longer heat [34]. Engine performance and emission
liquid penetration and worse atomization values substantially depend on LHV of fuels.
compared to diesel fuel [29 - 32]. Flash point Low temperature properties are characterized as
(FP) is the lowest temperature at which a liquid the ability of a fuel to resist solidification at sub-
can form an ignitable mixture in air near its ambient temperatures. The low temperature
surface, where its measurement requires an properties are usually determined by pour point
ignition source. As FP of a volatile material is (PP) [35]. Fuel properties of B100 and
the lowest temperature at which vapors of a fluid B100+EDTA are shown in Table 2.
134 International Journal of Automotive Engineering and Technologies, IJAET 8 (3) 140-149
2.4. Engine performance and emission measure exhaust emissions. Emission data were
determination procedure collected via a computer program. Accuracy
values of the gas analyzer are±10 ppm for CO,
Engine performance and emission experiments
±1 ppm for NOx, ±0.5% vol. for CO2, ±10% for
were conducted on a single cylinder, four stroke,
UHC. Smoke emissions were analyzed by a
water cooled, naturally aspirated, direct
model 6500 Wager Digital Smoke meter of
injection diesel engine. CR adjustment was
which accuracy is + OR - 1.0% nominal one
conducted via a harmonic drive mechanism
digit. The control unit is initially calibrated
driven by an CR adjustment by tilting a
under clear stack conditions with checks at 0%
“multilink” mechanism connected to the
connecting rod and crankshaft. As the harmonic and 100% opacity. The accuracy of the unit is
verified by use of the 2 neutral density filter
drive mechanism rotates in the clockwise
supplied with the system.
direction, the CR of the engine decreases due to
the downward movement of the piston or vice Table 3. Technical specifications of the test engine
versa (Figure 4). There is an CR adjuster on the Specifications Descriptions
engine block which rotates the harmonic drive Configuration Single cylinder
Type Direct injection diesel
mechanism. When the adjuster is twisted in anti- Displacement 661 cc
clockwise direction, the CR increases and the Bore 87.5 mm
CR reading is taken from a scale carved onto the Stroke 110 mm
block. CR can also be changed while the engine Injection variation 0-25º BTDC
is in operation. An eddy current type CR range 12:1-18:1
Power 4.8 HP @ 1500 rpm
dynamometer with 185 mm arm length was used Coolant Water
to load (kg) the engine via electromagnetic Aspiration Naturally
forces. Technical specifications of the engine
are given in Table 3. Schematic representation
of diesel engine test rig is shown in Figure 5.
t : Brake thermal efficiency (%); LHVf: Lower 2.4.3. Brake specific energy consumption
heating value of the fuel (MJ/kg); mf: mass flow (BSEC)
rate of the fuel (kg/h). BSEC may be computed Variations of BSEC with respect to engine load
as shown below: for B100 and B100+EDTA are shown in Figure
7. In general, BSEC values were found to
BSEC
LHV f *mf
(3)
diminish with the increase of load under various
BP CRs for both fuel modes. In terms of BSEC,
average B100 values were 18.8, 16.8, 15.3
2.4.1. Uncertainty analysis (kJ/kWs) whereas they were 10.1, 9.5, 8.4
Perturbation techniques were utilized to conduct (kJ/kWs) for B100+EDTA under CRs of 16, 17
uncertainty analysis [38] of performance and and 18, respectively. Increment in CR leads to
parameters ( t and BSEC). t errors were 1.7% higher in-cylinder temperature and pressures
which shorten ignition delay time and yield
and 3.1%; BSEC errors were 1.6% and 3.1% for
rapid flame propagation. Under these
B100 and B100+EDTA, respectively. Relative
conditions, lesser fuel injection is sufficient to
errors of variables are shown in Table 4.
achieve the same performance parameters
Table 4. Relative errors of variables compared to lower CR values which entails
Variable Relative error lower fuel consumption. Lower BSEC under
Load 0.6% B100+EDTA mode may be due to extra oxygen
Speed 0.6%
Fuel flow rate 1.2% and hydrogen contents which may bring about
LHV 1% shortened ignition delay, rapid and more
CO, CO2, UHC, NOx, Smoke 3.2% complete combustion compared to that of B100.
2.4.2. Brake thermal efficiency ( t
Variations of t with respect to engine load for
B100 and B100+EDTA are indicated in Figure
6. For both fuel modes, t values were prone to
increase as load and CR were elevated. Among
fuel modes, B100+EDTA depicted higher
average t values of 24.3%, 26.3% and 27.8%
whereas they were 18.3%, 19.4% and 20.3% for
B100 under CRs of 16, 17 and 18, respectively
at IT of 22º BTDC. As CR increases, augmented Figure 7. BSEC-load variation for both fuel modes under
in-cylinder temperature and pressure yield fuels variable conditions
to undergo more complete combustion which 2.4.4. Exhaust gas temperature (Te)
leads to higher t values for both fuel modes.
Variations of Te with respect to engine load for
Besides, B100+EDTA depicted superior B100 and B100+EDTA are demonstrated in
performance in comparison to that of B100 due Figure 8. As the load increases, engine performs
to its higher heating value and cetane number. higher t values which also cause increased Te
values for both fuel modes under all CRs. It was
found that, Te results were inversely
proportional to CR values. Average Te values
were 227.2ºC, 201.8ºC and 176.7ºC for
B100+EDTA and 289.3ºC, 278.4ºC and
260.6ºC for B100 at CRs of 16, 17 and 18,
respectively. This may be due to lower calorific
value and CN of B100 which cause longer
ignition delay and late combustion initiation that
Figure 6. t -load variation for both fuel modes under lead to shorter power generation duration
variable conditions compared to B100+EDTA. CR adjustment from
International Journal of Automotive Engineering and Technologies, IJAET 8 (3) 140-149 145
16 to 18 also yields more mixture take part in for both fuel modes. Average CO values were
combustion process which caters lower exhaust 125, 117 and 97 (ppm) for B100; 79, 70 and 59
gases and exhaust gas temperatures. (ppm) for B100+EDTA under CRs of 16, 17 and
18, respectively. UHC values of 128, 119 and 99
(ppm) for B100; 82, 75 and 62 (ppm) for
B100+EDTA were obtained under CRs of 16,
17 and 18, respectively. High CN and LHV of
B100+EDTA ensure improved flame
propagation and in-cylinder temperature to rise
rapidly and more complete combustion with
comparison to that of B100.
also be made for CR increment. NOx emissions for B100+EDTA; 19%, 17% and 16% for B100
also depict similar trend with those of CO2. As under CRs of 16, 17 and 18, respectively. High
the load and CR increase, combustion oxygen, hydrogen content and superior LHV
temperature also increases due to high fuel and CN of B100+EDTA stimulate more
injection quantities and in-cylinder temperature. complete combustion and provide diminished
Because NOx is largely dependent to end- soot formation.
combustion temperature, increment in NOx
becomes inevitable. This interpretation may be
made for CR increment as well. So, NOx values
are found to be 184, 191 and 206 (ppm) for
B100+EDTA; 104, 110 and 140 (ppm) for B100
under CRs of 16, 17 and 18, respectively.
2.4.7. Soot formation
Variations of exhaust smoke opacity (soot
formation) with respect to engine load for B100
and B100+EDTA are shown in Figure 13. Figure 13. Smoke opacity-load variation for both fuel
Particulate matters suspended in the exhaust gas modes under variable conditions
ambient form soot due to inadequate oxygen 3. Cost Analysis
(incomplete combustion) in the cylinder. Thus,
higher fuel consumption at high loads causes Table 5 depicts the cost analysis of this study.
more smoke to be formed and increased smoke The total cost of 5.03 L of biodiesel production
opacity for both fuel modes. However, soot from waste sun flower oil is $6.59 which
formation is prone to descend with the increase corresponds to $1.17/L. Considering $1.11/L
in CR. Higher CR means more suitable current unit price of diesel fuel in Turkey, it is
conditions for complete combustion due to high clear that, in general, the cost of the sun flower
in-cylinder temperature and pressure. Average methyl ester with EDTA is comparable with that
smoke opacity values were 15%, 12% and 10% of the diesel fuel.
Table 5. Cost analysis of the experimental study
Substance Amount Used Unit Price Cost
Waste sunflower oil 4550 g -
EDTA 0.0665 g $25.19/100 g $0.016
NaOH 22.8 g $21.35/500 g $0.97
Methanol 1.03 L $4.77/1 L $4.91
TOTAL $6.59
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