Fuel 85 (2006) 298305

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Diesel engine performance and emission characteristics

of biodiesel produced by the peroxidation process
Cherng-Yuan Lin*, Hsiu-An Lin
Department of Marine Engineering, National Taiwan Ocean University, No. 2, Pei-Ning Road, Keelung 20224, Taiwan, ROC
Received 8 March 2005; received in revised form 16 May 2005; accepted 21 May 2005
Available online 22 June 2005

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

layer in the stratosphere, forms nitric acid, and irritates the

eyes, throat and respiratory system. PMs, which make up of
about 580% soluble organic fractions (SOF), can initiate
pathological changes in human respiratory system. In
addition, the poly-aromatic hydrocarbons (PAH) compositions in the SOF compounds are suspected of being
carcinogenic agents [2].
Biodiesel is considered a promising alternative fuel for
the reduction of pollution from diesel engines, boilers and
other combustion equipment. Compared to fossil diesel fuel,
biodiesel has several superior combustion characteristics.
For example, when biodiesel is used as an engine fuel, its
approximately 10 wt% of oxygen content may promote a
more complete combustion and effectively reduce the
production of unburned hydrocarbons (UHC), CO as well
as suspended aerosol carbon granules [3]. In addition, since
biodiesel does not contain carcinogens such as polyaromatic hydrocarbons and nitrous poly-aromatic hydrocarbons (nPAH), it produces pollutants that are less

C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

detrimental to human health [4] when burned. Also, fuel

characteristics of biodiesel are approximately the same as
those of fossil diesel fuel and thus may be directly used as a
fuel for diesel engines without any prior modification of the
design or equipment. In fact, the Environment Protection
Agency of the United States (USEPA) and the Food and
Drug Administration of the United States (FDA) have
recognized biodiesel as a clean alternative fuel or fuel
additive.
Vegetable oils such as soybean oil, corn oil, palm oil,
peanut oil, sunflower seed oil, rapeseed oil, and others can
be used as raw material to produce biodiesel. Used frying
oil or waste cooking oil can also be used for the production
of biodiesel to reduce raw material cost [5]. There are
several technologies for manufacturing biodiesel, including
transesterification or alcoholysis, amidation of fats or oils
with diethylamine as well as transesterification in
supercritical methanol [6]. Transesterification is the most
frequently applied method of industrial biodiesel production. Three types of catalysts, such as a strong alkali, a
strong acid or an enzyme, can be used in the manufacturing
process of the transesterification method. The use of a
strong alkali as a catalyst in the transesterification process
has the advantages of a shorter reaction time and lesser
amount of required catalyst. Hence, the strong alkali
catalyst is widely used in the transesterification process to
produce biodiesel. In contrast, a strong acid catalyst
generally needs a longer reaction time, but is adaptable
to more kinds of reactant mixtures. For example, reactants
containing a small amount of water and free fatty acids can
still be transesterified to form biodiesel if a strong acid
catalyst is used.
Although biodiesel has many advantages when it comes
to fuel properties, it still has several properties that need to
be improved, such as its lower calorific value, lower
horsepower output, and its comparatively higher emission
of nitrogen oxides. Monyem et al. [7] believed that fuel
properties of biodiesel might be affected by oxidation after
the biodiesel was stored for a period of time. They heated a
commercial biodiesel while bubbling oxygen through it to
simulate storage conditions. They found that after this
process the commercial biodiesel had a shorter ignition
delay and lower HC emission. In contrast, this study intends
to promote the engine performance and emission characteristics of biodiesel by improving its reacting process
through applying a peroxidation technique in combination
with the transesterification process.
The peroxidation technique is a technique to reduce
compounds of high molecular weight. It is mostly applied in
cosmetics, medicine, pharmaceutics and food industries.
Either hydrogen peroxide or an ozone compound can be
used in the peroxidation process. The peroxidation process
may break the molecular bonds of polysaccharide. The
reduction of viscosity and the increase of fluidity of
polysaccharide through this peroxidation process will result
in the enhancement of the solubility of polysaccharide [8].

299

In this study, the transesterification process combined with

the peroxidation technique was used to convert soybean oil
into biodiesel to improve its fuel properties, and the engine
performance and emission characteristics of the biodiesel
thus produced were then tested and analyzed.

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.

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C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

Table 2
Properties of sample 1 biodiesel and sample 2 biodiesel
Item

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

3. Results and discussions

Fig. 1. Experimental set-up of this study.

The experimental set-up and measuring instruments are

shown in Fig. 1. The fuel properties of the ASTM No. 2D
diesel fuel, commercial biodiesel, samples 1 and 2
biodiesels that were used as the test fuels in this study, are
listed in Tables 13. The ASTM No. 2D was obtained from
the Chinese Petroleum Company in Taiwan. The commercial biodiesel was provided by a large biodiesel producer in
the USA, which was produced from fresh soybean oil and
methyl alcohol via a transesterification reaction. The engine
experiment was carried out under fixed engine torque at
10 kgf and varied engine speeds from 850 to 2000 rpm to
simulate medium engine load conditions. Each experiment
was repeated three to five times to calculate the mean value
of the experimental data. The experimental uncertainties for
NOx, CO, CO2, O2, excess air, and exhaust gas temperature
were 2.95, 3.51, 1.58, 0.04, 2.24, and 0.45, respectively.
Table 1
Properties of commercial biodiesel
Item
Product

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

A hydrogen peroxide agent, which has a strong chemical

activity, was used to react with sample 1 biodiesel in the
peroxidation process. Part of the compound of unsaturated
fatty acids in sample 1 biodesiel was susceptible to attack by
the oxygen content of the hydrogen peroxide, and thus
became saturated fatty acids. The saturated carbon bonds of
sample 1 biodiesel was 16.6 wt%. After the peroxidation
process, the saturated carbon bonds of sample 2 biodiesel
became 18.2 wt%. This implies that the saturated carbon
bonds of the biodiesel increased by 1.6 wt% after the
peroxidation process. When sample 1 biodiesel, which was
produced from the transesterification process, reacted with
the hydrogen peroxide during the peroxidation process, the
hydrogen peroxide component was more likely to attack the
p bond in the unsaturated carbon bonds of methyl esters of
sample 1 biodiesel. This chemical reaction incurred
electrophilic addition on the methyl esters. The hydroxyl
group of the hydrogen peroxide was then attached to the
original positions of the double bonds of methyl esters. The
unsaturated carbon bonds of sample 1 biodiesel thereafter
became saturated carbon bonds. Consequently, the saturated
carbon bonds increased from 16.59 wt% for sample 1
biodiesel to 18.15 wt% for sample 2 biodiesel by 1.56 wt%.
Fig. 2 shows the fuel consumption rates of the four
different kinds of fuels, indicating that ASTM No. 2D
Table 3
Properties of ASTM No. 2D diesel fuel
Item

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

C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

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)

Fuel Consumption Rate (Kg/hr)

301

200.0
150.0

ASTM No.2D diesel

Commercial biodiesel

100.0

Sample No.1 biodiesel

Sample No.2 biodiesel

1.00

Sample No.1 biodiesel

Sample No.2 biodiesel

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.

diesel fuel, commercial biodiesel, sample 1 biodiesel and

sample 2 biodiesel increased roughly in proportion with
engine speed under fixed engine torque conditions. This is
attributed to the fact that when engine speed rises, the
friction horsepower increased according to the drop in the
mechanical efficiency to maintain a fixed torque output
[9], leading to an increase in the fuel consumption rate. At
the same time, a lower fuel consumption rate is required
for a fuel with a higher heating value. The ASTM No. 2D
diesel has the highest heating value among the four
fuels tested, which being 11,035.7 cal/g as shown in
Tables 13. Consequently, the ASTM No. 2D diesel fuel
had the lowest fuel consumption rate among the four
fuels. Sample 1 biodiesel consumed less fuel than either
sample 2 biodiesel or the commercial biodiesel in
attaining the same engine horsepower output. This is
owed to the fact that its heating value was larger than the
other two biodiesels. The fuel properties of the peroxidised biodiesel such as cetane index, heating value,
kinematical viscosity, etc. are close to those of the ASTM
No. 2D diesel fuel, as shown in Tables 13. Hence, the
peroxidised biodiesel can be used directly as an
alternative fuel to the ASTM No. 2D diesel fuel without
having to modify the engine systems.
The curves in Fig. 3 show that the brake specific fuel
consumption (bsfc) of the four different kinds of fuels
decreased slightly with the increase in engine speed under
constant engine torque. The bsfc is defined as the ratio of the
fuel consumption rate to the engine brake horsepower
output [10]. When the engine speed increases, and if the
increase in the fuel consumption rate is lower than that
of the corresponding brake horsepower output, then a
decreasing tendency of the bsfc appears, as shown in Fig. 3.
It must be noted that ASTM No. 2D diesel has the lowest

bsfc value. This is primarily due to the fact that ASTM

No. 2D diesel has the highest heating value among the four
fuels, and needed the lowest fuel consumption rate for
achieving the same engine brake horsepower output as the
other three fuels. Sample 1 biodiesel appeared to have a
lower bsfc value than either sample 2 biodiesel or the
commercial biodiesel. This was primarily due to its lower
fuel consumption rate under the same engine brake
horsepower output condition, compared to the other two
biodiesels, as shown in Fig. 2. In contrast, the commercial
biodiesel had the lowest heating value and the largest fuel
consumption rate, requiring the largest bsfc among the four
fuels, as shown in Fig. 3.
The brake thermal efficiency for the four different fuels
under constant engine torque and varied engine speeds is
shown in Fig. 4. The brake thermal efficiency is defined as
the brake horsepower output divided by the rate of heat
released from the fuel burning process. Samples 1 and 2
biodiesels had larger brake thermal efficiency than ASTM
No. 2D diesel. The oxygen contents of the biodiesels
improved their fuel burning characteristics. Moreover, fuel
with a higher cetane index has a superior compressionignition quality in diesel engines and thus better combustion
characteristics. The cetane indices of ASTM No. 2D diesel,
commercial biodiesel, samples 1 and 2 biodiesels are 50.9,
45.8, 49.9 and 48.8, respectively. Hence, commercial
biodiesel with a significantly lower cetane index appeared
to have the lowest brake thermal efficiency among the four
fuels. In contrast, the cetane indices of samples 1 and 2
biodiesels and ASTM No. 2D diesel are comparable to each
other, even though the oxygen content of the former two
fuels are much higher than the latter. Consequently, samples
1 and 2 biodiesels had a higher brake thermal efficiency than
ASTM No. 2D diesel.

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C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

0.450

Brake Thermal Efficiency (%)

0.400

0.350

0.300

0.250

ASTM No.2D diesel

Commercial biodiesel
Sample No.1 biodiesel

0.200

Sample No.2 biodiesel

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.

Fig. 5 shows the fuel/air equivalence ratio of the four

fuels under varied engine speeds and constant engine
torque. The equivalence ratio is defined as the actual fuel to
air ratio divided by the stoichiometric fuel to air ratio on a
mass basis [10]. An equivalence ratio larger than 1 indicates
a fuel-rich burning condition, while a smaller than 1 ratio
indicates a fuel-lean condition [11]. The increase in engine
speed requires a larger fuel consumption rate and therefore a
larger equivalence ratio. Sample 2 biodiesel has the lowest
0.40

fuel/air equivalence ratio in comparison with the other three

fuels, as shown in Fig. 4. Sample 2 biodiesel, which was
produced by transesterification followed by the peroxidation
process, has a higher oxygen content than either the
commercial biodiesel or sample 1 biodiesel, as shown in
Tables 1 and 2. Hence, a larger amount of oxygen and more
excess air were found in the reactant mixture of sample 2
biodiesel in comparison with the other two biodiesels.
Moreover, the elemental carbon contents of ASTM No. 2D
diesel, commercial biodiesel, and samples 1 and 2 biodiesels
are 86.13, 76.96, 77.3 and 76.75%, respectively, as shown in
Tables 13. A fuel with lower carbon content indicates it has
a lower rate of fuel consumption and a lower heating value.
Consequently, sample 2 biodiesel had the lowest fuel/air
equivalence ratio among the four fuels, as shown in Fig. 4.
The carbon dioxide (CO2) emission index for using
samples 1 and 2 biodiesels, ASTM No. 2D diesel and the
commercial biodiesel as the engine test fuels under the
condition of constant engine torque and varied engine
speeds are shown in Fig. 6. The CO2 emission index is
defined as the CO 2 emission (%) divided by the
corresponding fuel consumption rate (in unit of g/h) [11].
The CO2 emission index decreased with the increase in
engine speed for these four fuels. The three kinds of
biodiesels had lower CO2 emission indices than ASTM No.
2D diesel. This is attributed to the fact that biodiesel is a low
carbon fuel and has a lower elemental carbon to hydrogen
ratio than diesel fuel. The burning of biodiesel with air will
therefore form lower CO2 emission than ASTM No. 2D
diesel. Moreover, the combustion of the sample 2 biodiesel
produced the lowest CO2 emission index among the four
fuels, as shown in Fig. 6. This is probably due to the fact that
this biodiesel has the lowest equivalence ratio, as shown in
Fig. 4, and also the fact that CO2 emission concentration
2.5

0.35
2.0

0.25
0.20
0.15

ASTM No.2D diesel

Commercial biodiesel

0.10

Sample No.1 biodiesel

CO 2 Emission Index (%/g/hr)

Equivalence Ratio ( )

0.30

1.5

1.0
ASTM No.2D diesel
Commercial biodiesel

0.5

Sample No.1 biodiesel

Sample No.2 biodiesel

0.05

Sample No.2 biodiesel

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.

C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

380

Exhaust Gas Temperture (C)

360
340
320
300
280
260
ASTM No.2D diesel

240

Commercial biodiesel

220

Sample No.1 biodiesel

Sample No.2 biodiesel

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)

decreases with the decrease of the equivalence ratio in the

range of less than 1 [10]. In addition, the carbon contents of
ASTM No. 2D diesel, sample 1 biodiesel, commercial
biodiesel, and sample 2 biodiesel are 86.13, 77.3, 76.95, and
76.75 wt%, respectively, as shown in Tables 13. The CO2
emission indices of these four fuels followed the same
sequence as their carbon contents. The ASTM No. 2D
diesel, which had the largest carbon content, is also shown
to have the largest CO2 emission indices in Fig. 6.
The exhaust gas temperatures for the various fuels are
compared in Fig. 7. The amount of injected fuel increases
with the engine speed in order to maintain a constant engine
torque output. Hence, the heat release rate and the exhaust
gas temperatures from burning these fuels rise with the
increase in engine speed. The burning of ASTM No. 2D
diesel was found to have the highest exhaust gas
temperature due to its highest heating value among these
four fuels. In addition, there were no obvious variances in
the exhaust gas temperatures among the biodiesel fuels.
Fig. 8 shows the carbon monoxide (CO) emission index
for the four different fuels under different engine speeds and
constant engine torque. The CO emission index is defined as
CO emission (ppm) divided by the corresponding fuel
consumption rate (in unit of g/h) [11]. It was found that the
CO emission index decreased with the increase in engine
speed. This is primarily due to the lower gas temperature in
the engine cylinder at lower engine speeds, which prevents
the CO component to be effectively converted to CO2.
However, the fuel/air equivalence ratio increased with the
increase in engine speed, resulting in an increased gas
temperature in the engine cylinder. This led to an increase in
the conversion rate of CO to CO2 and hence a lower CO
emission index at higher engine speeds. In addition, the
three kinds of biodiesels were found to emit significantly

303

Commercial biodiesel
Sample No.1 biodiesel

250

Sample No.2 biodiesel

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.

lower CO concentrations compared with that of ASTM No.

2D diesel. The biodiesels contain about 10% oxygen on a
mass base and have a lower carbon content than the ASTM
No. 2D diesel. Moreover, the oxygen content in the
biodiesel enhances their combustion process, thereby
reducing the formation of CO emission. The burning of
sample 2 biodiesel appeared to emit the lowest CO
emission, primarily owing to its having the lowest carbon
content, 76.75 wt%, among the four fuels, as shown in
Tables 13. The ASTM No. 2D diesel had the highest
carbon content, 86.13 wt%, and therefore exhausted the
highest CO concentration compared to the other three fuels.
Since the ignition delay can be shortened and the
combustion efficiency enhanced with the oxygen content
in the fuel, the CO emission can thus be further reduced
[12]. The CO emission indices of the four fuels followed the
same sequence of their carbon contents. Therefore,
biodiesel can be used as a clean, lower carbon alternative
fuel to replace fossil fuel for diesel engines and other
combustion equipment.
The nitrogen oxides (NOx) emission index for the various
fuels under constant engine torque and varied engine speeds
is shown in Fig. 9. The NOx emission index is defined as
NOx emission (ppm) divided by the corresponding fuel
consumption rate [11]. The NOx emission indices were
found to decrease with the increase in engine speed. This is
primarily due to the increase in volumetric efficiency and
gas flow motion within the engine cylinder under higher
engine speeds, which leads to a faster mixing between fuel
and air, and a shorter ignition delay. The volumetric
efficiency is defined as the mass of air and fuel inducted into
the diesel engine cylinder divided by the total mass that
occupies the displacement volume, at intake manifold
density [10]. As a result, a large mass flow of fuel and air
inducted into the engine cylinder at larger engine speed

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C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

under the operating condition of lower engine speeds.

Hence the comparatively higher NOx emission index for
engine speeds between 850 and 1000 rpm.

300

NOx Emission Index (ppm/g/hr)

250

ASTM No.2D diesel

Commercial biodiesel

200

Sample No.1 biodiesel

Sample No.2 biodiesel

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.

could cause an increase of the volumetric efficiency. The

reaction time of each engine cycle was thereafter reduced so
that the residence time of the high gas temperature within
the cylinder was shortened. This led to lower NOx emission
under higher engine speed. In addition, biodiesels contain
oxygen components ranging from 9.09 wt% for sample 1
biodiesel to 9.94 wt% for sample 2 biodiesel. So it is evident
that there is higher oxygen content available in the biodiesel
to react with the nitrogen component in the surrounding air,
resulting in a larger amount of NOx formation [13,14]. The
commercial biodiesel and sample 1 biodiesel were found to
emit a larger amount of NOx, while sample 2 biodiesel
produced the lowest amount of NOx emission. Diesel
engines are mostly operated in fuel-lean burning conditions.
The NOx emission decreases with the decrease in the fuel to
air ratio under fuel-lean burning conditions of a diesel
engine [15]. Hence, sample 2 biodiesel required the lowest
fuel-to-air equivalence ratio as shown in Fig. 5, and emitted
the lowest NOx concentration among these four fuels in
Fig. 9. Moreover, the proportions of saturated carbon bonds
are 16.6 wt% for sample 1 biodiesel and 18.2 wt% for
sample 2 biodiesel, after the peroxidation process. This
implies that the saturated carbon bonds for sample 2
biodiesel increased significantly, by 1.6 wt%. The burning
of biodiesel with a larger weight proportion of saturated
carbon bonds could cause a reduction in NOx emission [4].
As a consequence, sample 2 biodiesel had the lowest NOx
emission index. In addition, the NOx emission index for
sample 2 biodiesel when operating the engine between 850
and 1000 rpm was somewhat larger than that of ASTM No.
2D diesel. This is probably because of the relatively higher
oxygen content of sample 2 biodiesel, which produced a
higher NOx formation, even at a lower burning gas
temperature and a lower mass flow rate of intake air,

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.

C.-Y. Lin, H.-A. Lin / Fuel 85 (2006) 298305

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