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Abstract
Biodiesel is an alternative fuel that is cleaner than petrodiesel. Biodiesel can be used directly as fuel for a diesel engine without having to
modify the engine system. It has the major advantages of having high biodegradability, excellent lubricity and no sulfur content. In this study,
the biodiesel produced by a transesterification technique was further reacted by using a peroxidation process. Four types of diesel fuel,
biodiesel with and without an additional peroxidation process, a commercial biodiesel and ASTM No. 2D diesel were compared for their fuel
properties, engine performance and emission characteristics. The experimental results show that the fuel consumption rate, brake thermal
efficiency, equivalence ratio, and exhaust gas temperature increased while the bsfc, emission indices of CO2, CO and NOx decreased with an
increase of engine speed. The three biodiesels showed a higher fuel consumption rate, bsfc, and brake thermal efficiency, while at the same
time exhibited lower emission indices of CO and CO2 as well as a lower exhaust gas temperature when compared to ASTM No. 2D diesel.
Moreover, the biodiesel produced with the additional peroxidation process was found to have an oxygen content, weight proportion of
saturated carbon bonds, fuel consumption rate, and bsfc that were higher than the biodiesel produced without the additional process; while at
the same time the brake thermal efficiency, equivalence ratio, and emission indices of CO2, CO and NOx were found to be lower. In
particular, biodiesel produced with the addition of the peroxidation process had the lowest equivalence ratio and emission indices of CO2, CO
and NOx among all of the four test fuels. Therefore, the peroxidation process can be used to effectively improve the fuel properties and reduce
emissions when biodiesel is used.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Diesel engine; Peroxidation process; Emission characteristics
1. Introduction
Pollutants from diesel engines include carbon monoxide
(CO), carbon dioxide (CO2), sulfur oxides (SOx), nitrogen
oxides (NOx), and particulate matter (PM). NOx and PM are
the two primary pollutants of diesel engines. Nitrogen
dioxide (NO2), a compound of NOx, has a strong capacity to
absorb infrared rays. NO2 is about 250 times more
threatening to global warming than CO2 at the same
concentration [1]. In addition, NO2 has the characteristics
of high stability and longevity (approximately 150 years) in
the atmosphere. The reaction of NOx with sunlight produces
photochemical smog. Moreover, NOx destroys the ozone
* Corresponding author. Tel./fax: C886 2 2462 2307.
E-mail address: lin7108@mail.ntou.edu.tw (C.-Y. Lin).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.05.018
299
2. Experimental details
In this study, soybean oil (used as raw oil) and methanol
in a molar proportion of 1:6 were reacted to produce
biodiesel. Then 1 wt% of NaOH of the soybean oil was
added as a catalyst in the transesterification reaction. A
mechanical stirrer to form sodium methoxide and water first
mixed the NaOH catalyst with methanol. The mixture of
sodium methoxide and water was then poured into a
reacting tank to mix with the soybean oil and stirred by a
homogenizer to obtain a transesterification reaction. The
reason for using methanol in this chemical reaction is
primarily due to its superior advantages of high solubility in
oil, fast reaction rate, good physical and chemical properties, and low cost. The reacting temperature of the
transesterification process was set at 60 8C, which is right
below the boiling temperature of methanol at 63 8C to
prevent the methanol from vaporizing from the reacting
mixture during the transesterification process. It took
50 min to complete the transesterification process. After
the completion of the transesterification process, the mixture
was separated into coarse biodiesel and glycerin by keeping
the mixture motionless, or by centrifuging the mixture. A
distillation method was then used to remove the un-reacted
methanol contained in the coarse biodiesel. This was
followed by adding 50 wt% of petroleum ether and
0.5 wt% of distilled water of the coarse biodiesel to mix
with the coarse biodiesel to remove other impurities in the
coarse biodiesel. The biodiesel obtained after this process
was termed sample 1 biodiesel in this study.
After this, a peroxidation technology was used to further
promote the fuel properties of sample 1. In using this
technology, 1% of hydrogen peroxide (H2O2) was then
added and stirred with sample 1 biodiesel in the reactor tank
at 60 8C. The reaction time of this peroxidation process was
10 min. Afterwards the un-reacted impurities and methanol
were removed by a distillation method, and sample 2
biodiesel was obtained.
The samples 1 and 2 biodiesels were then tested for their
performance in a diesel engine and for their emission
characteristics. A four-cylinder, four-stroke, naturally
aspirated, direct-injection diesel engine was used as the
test engine in this experiment. The displacement volume of
this engine is 3856 cm3. An eddy-current dynamometer in
combination with the diesel engine was used to control the
engine torque in the range from 0 to 18 kgf. A gas analyzer
measured the emissions from the diesel engine, and the
temperature of the exhaust gas was measured by a K-type
thermocouple.
300
Property
Unit
Biodiesel sample
No. 1
No. 2
Cetane index
C, %
H, %
O, %
S, %
Saturated carbon bonds
Heating value
49.9
77.3
11.62
9.09
0
16.6
9715.2
48.9
76.75
11.48
9.94
0
18.2
9687.3
wt%
wt%
wt%
wt%
wt%
Cal/g
Property
Unit
Biodiesel in market
Test Method
Cetane index
C, %
H, %
O, %
S, %
Water
Ash
Carbon residue
Heating value
45.8
76.96
11.85
9.41
0.017
0.026
0.00
0.04
9491.9
ASTM D976
wt%
wt%
wt%
wt%
wt%
Cal/g
ASTM D4294
ASTM E1064
ASTM D976
ASTM D524
Property
Unit
Cetane index
C, %
H, %
S, %
Distillation
temperature
50.9
86.13
13.93
0.34
171
215
228
257
317
338
352
98
1.6
11035.7
wt%
wt%
wt%
8C (IBP)
8C (10 vol%)
8C (20 vol%)
8C (50 vol%)
8C (90 vol%)
8C (95 vol%)
8C (End point)
vol%
vol%
cal/g
Recovery
Residue
Heating value
Test method
ASTM D976
ASTM D4294
ASTM D86
6.00
350.0
300.0
5.00
250.0
4.00
3.00
ASTM No.2D diesel
2.00
Commercial biodiesel
bsfc (g/kw-hr)
301
200.0
150.0
100.0
1.00
50.0
0.0
0.00
850
1000
1200
1400
1600
Enging Speed (rpm)
1800
2000
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 2. Fuel consumption rate of using biodiesels and diesel as the diesel
engine fuels under constant engine torque 10 kgf m and varied engine
speeds.
Fig. 3. Brake specific fuel consumption (bsfc) of using biodiesels and diesel
as the diesel engine fuels under constant engine torque of 10 kgf m and
varied engine speeds.
302
0.450
0.400
0.350
0.300
0.250
0.200
0.150
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 4. Brake thermal efficiency of using biodiesels and diesel as the diesel
engine fuels under constant engine torque of 10 kgf m and varied engine
speeds.
0.35
2.0
0.25
0.20
0.15
0.10
Equivalence Ratio ( )
0.30
1.5
1.0
ASTM No.2D diesel
Commercial biodiesel
0.5
0.05
0.0
0.00
850
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 5. Equivalence ratio of using biodiesels and diesel as the diesel engine
fuels under constant engine torque of 10 kgf m and varied engine speeds.
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 6. CO2 emission index from a diesel engine when using biodiesels and
diesel as fuels under constant engine torque of 10 kgf m and varied engine
speeds.
380
360
340
320
300
280
260
ASTM No.2D diesel
240
Commercial biodiesel
220
200
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 7. Exhaust gas temperature from a diesel engine when using biodiesels
and diesel as fuels under constant engine torque of 10 kgf m and varied
engine speeds.
350
ASTM No.2D diesel
300
CO Emission Index (ppm/g/hr)
303
Commercial biodiesel
Sample No.1 biodiesel
250
200
150
100
50
0
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 8. CO emission index from a diesel engine when using biodiesels and
diesel as fuels under constant engine torque of 10 kgf m and varied engine
speeds.
304
300
250
200
150
100
50
850
1000
1200
1400
1600
Engine Speed (rpm)
1800
2000
Fig. 9. NOx emission index from a diesel engine when using biodiesels and
diesel as fuels under constant engine torque of 10 kgf m and varied engine
speeds.
4. Conclusions
In the industry, biodiesel is mostly produced by a
transesterification technique. In this study, this biodiesel
was further reacted by using the peroxidation process. The
fuel properties, engine performance and emission characteristics of ASTM No. 2D diesel, a commercial biodiesel,
biodiesel with and without the peroxidation process were
analyzed and compared. The experimental results of this
study can be summarized as follows.
1. The increase in engine speed caused an increase in fuel
consumption rate, brake thermal efficiency, equivalence
ratio, and exhaust gas temperature, while at the same
time decreasing the bsfc, emission indices of CO2, CO
and the NOx for the four fuels.
2. In comparison with ASTM No. 2D diesel, the three kinds
of biodiesels appeared to have a higher fuel consumption
rate, bsfc, and brake thermal efficiency, while the
emission indices of CO2 and CO as well as the exhaust
gas temperature were lower.
3. The oxygen content was significantly increased from
9.09 to 9.94 wt%, and the saturated carbon bonds
increased significantly by 1.6 wt%, from 16.6 to
18.2 wt%, for the biodiesel produced with the additional
peroxidation process.
4. The biodiesel that was produced using the additional
peroxidation process was also observed to have a higher
fuel consumption rate and bsfc, but a lower brake
thermal efficiency, equivalence ratio, as well as lower
emission indices of CO2, CO and NOx than those of
biodiesel produced without this peroxidation process.
5. Among all the four test fuels, the biodiesel with the
additional peroxidation process appeared to have the
lowest equivalence ratio and CO2, CO and NOx emission
indices. It is evident that the peroxidation technique has
been shown to be capable of effectively improving fuel
properties and reducing the emission pollution of
biodiesel.
Acknowledgements
The authors gratefully acknowledge the financial
support for this study by the National Science Council
of Taiwan, ROC under Project Contract No. NSC 902212-E-019-010.
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