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Published 08/18/2017
Copyright © 2017 SAE International
doi:10.4271/2017-01-9377
ABSTRACT
Biodiesel as an alternative diesel fuel prepared from vegetable oils or animal fats has attracted more and more attention because of its
renewable and environmental friendly nature. Many recent studies shows that 20% proportion of biodiesel-diesel blend (B20) can
substantially reduce the hydrocarbon (HC), carbon monoxide (CO) and smoke emissions. However, there is a slight increase in NOx
emission for B20 than that of diesel and it was a barrier to market expansion. The addition of antioxidant additives was the most
effective method to mitigate the NOx emission. Hence, in this paper experimental investigation has been carried out to mitigate the
NOx emission in Annona biodiesel (A20) operated diesel by addition of antioxidant additives. The antioxidant additives such as
p-phenylenediamine, A-tocopherol acetate and L-ascorbic acid were used in the present investigation. In recent years Annona biodiesel
has been considered as potential novel renewable energy source in India. Therefore in this experimental investigation was conducted to
improve the A20 (7) (20% of annona methyl ester with 80% of diesel) with the help of antioxidant additives. It was evidently proved
from the experimental investigation that use of antioxidant additive was effective in controlling the NOx emission in diesel engine.
Result shows that 250mg concentration of p-phenylenediamine additive with A20 blend was optimum for NOx mitigation up to 25.7%
when compared to that of diesel without any major modification.
KEYWORDS: Annona methyl ester, NOx mitigation, Antioxidant additives, Emissions, Diesel Engine
CITATION: Rajendran, S., "NOx Emission Reduction in Annona Biodiesel Engine by Means of Antioxidant Additives," SAE Int. J. Fuels
Lubr. 10(3):2017, doi:10.4271/2017-01-9377.
INTRODUCTION Jatropha biodiesel blends was lower and there is a slight increase in
BSFC of Jatropha biodiesel blends than that of diesel. Further the
Alternative fuels have been widely used in the internal combustion
HC, CO and smoke emissions were lower for Jatropha biodiesel
engines due to extensive research in finding alternative sources for
blends than that of diesel but at the expense of increase in NOx[10].
fossil based fuels. Vegetable oils, biodiesel, simple alcohols such as
methanol and ethanol and blended fuels are utilized in combustion
engines. The CO, HC and smoke emissions were reduced but NOx NOx Mechanism
emission was increased with vegetable oil blends than that of diesel As the use of biodiesel has increased tremendously the rise in NOx
fuel. Further, the engine performance with vegetable oil blend or emission can became a significant barrier to market expansion. For
biodiesel was similar to that of diesel fuel [1, 2, 3, 4, 5, 6]. pure 100% biodiesel increase the NOx emission by 13% than that of
diesel. During combustion, the NOx is generated by three mechanism
such as thermal, prompt and fuel. High combustion temperature
EFFECT OF BIODIESEL DIESEL BLENDS
(1700K) breaks the strong triple bond of nitrogen molecules and form
The A20 blend shows better performance and lower exhaust high less reactive atomic nitrogen, then it reacts with the oxygen and
emissions. Further, the CO, HC, and smoke emissions were reduced generates thermal NOx. Further the formation of free radicals in the
considerably. However, the NOx emission was slightly increased for flame front of the HC flames leads to the rapid production of prompt
the various proportions of Annona methyl ester (AME) [7]. The brake NOx. The fuel NOx is formed by the reaction of nitrogen bond in the
specific fuel consumption (BSFC) for Ceibapentandra biodiesel fuel with the oxygen during combustion process. Among these three
blends (CPB10) was higher than that of diesel and CO, HC and mechanisms, thermal and prompt NOx are the dominant mechanisms
smoke emissions were reduced for all biodiesel blends. Further, the in biodiesel operated diesel engine since biodiesel does not contain
NOx and CO2 emission were increased for CPB10 when compared to fuel bond nitrogen. The thermal mechanism is unaffected by fuel
that of diesel [8]. The brake specific energy consumption (BSEC) of chemistry, whereas the prompt mechanism is sensitive to free radical
rice bran oil was higher than that of all blends at all loads and in the reaction zone. Numerous reasons have been proposed for
viscosity, better combustion and lesser emission than that of other biodiesel NOx effect; however the exact cause is still unclear. The
blends of rice bran oil [9]. The Brake thermal efficiency (BTE) of development of improved NOx reduction technologies is therefore
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critical to the global environment. Hence the antioxidants are very in BSFC by 0.43% and 0.57%, respectively and increase in BTE by
effective in controlling the NOx emission and it has potential 0.36% and 0.45% respectively when compared to that of neat
antioxidant properties to supress the free radical formation. [11, 12, biodiesel. Further, the NOx emission for both BHT and MBEBP
13, 18, 19] blends were reduced by 5.91% and 5.27% respectively, but there was
a significant increase of HC, smoke and CO emissions [20]. The
Effect of Antioxidant Additives antioxidant was effectively controlling the NOx emission. Further, the
The L-ascorbic acid antioxidant additive was mixed in various addition of 0.15%-m DPPD additive in JB5, JB10, JB15 and JB20
proportions such as 100-400 mg with methyl ester of cottonseed oil showed NOx emission reduction of 8.03%, 3.503%, 13.65% and
(MECSO). The NOx and HC emissions for LA300 with MECSO 16.54% respectively, when compared to that of biodiesel blends
were reduced by 9.31% and 23.62% respectively. Further, the CO and without antioxidant additive [21]. The addition of
smoke emissions were higher to all the mixtures of antioxidant butylatedhydroxyanisole was effectively controlling the NOx
additive with MECSO when compared to that of neat biodiesel [11]. emission, but the other antioxidants were not reducing the NOx
The various antioxidant additives such as L-ascorbic acid, α- emission [22]. The performance characteristics for soybean biodiesel
tocopherol acetate, butylatedhydroxytoluene, p-phenylenediamine operated diesel engine were not influenced by the addition of
and ethylenediamine were used. The NOx emission for 0.025%-m antioxidants. Further the addition antioxidant additives with soybean
concentration of p-phenylenediamine was reduced by 43.55% when biodiesel was reduced the NOx emission efficiently decreased more
compared to other antioxidants additives at 0.025%-m concentration. than that of biodiesel fuel without antioxidant additive [23].
Further, the HC and CO emissions were slightly increased with the
addition of antioxidant additives [12]. The antioxidant additives, N, Chemistry of Antioxidant
N′-diphenyl-1, 4-phenylenediamine (DPPD) and N-phenyl-1, Addition of small amounts of antioxidants into the biodiesel suppress
4-phenylenediamine (NPPD) were tested in a diesel engine. The the free radical formation of the hydrogen is released from the weak
maximum NO reduction for DPPD and NPPD additives were 9.35% OH (phenols,hydrouinones) and NH (aromatic amines, diamines)
and 4.06% respectively when compared to that of B20 at 75% load. blends of antioxidant [13]. Lipid oxidation reaction, such as these in
Further, the aromatic amine antioxidants were reduced the NO biodiesel, are intitated by the formation of peroxides. A requirement
emission below the level of conventional diesel engine [13]. The four for this reaction is free radicals, which is formed from oxygen present
synthetic antioxidants such as butylatedhydroxyanisole (BHA), in the atmosphere. The most effective way to inhibit the oxidation of
butylatedhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ) biodiesel is to limit its exposure to oxygen by adding antioxidants to
and 2-ethylhexyl nitrate (EHN) were tested on a Land Rover the FAME that can dispose of the formed oxygen radicals. The
turbocharged DI diesel engine. The highest NOx emission reduction hydroxyl (-OH) group of the antioxidant is active so that hydrogen is
was found at EHN followed by BHT and BHA. The lowest NOx abstracted from -OH by donating a hydrogen to hydroxyl. This
emission was observed for TBHQ [14]. The oxidation stability condition leads to a quirere live structure of the antioxidant, which a
increases with the increase of antioxidant additive proportion and the significantly more stable than the radicals [20].
NOx emission of BHT100 with MENO is reduced by 19.99% at full
load condition when compared to that of neat biodiesel. However, the Reaction: OH+ROO. - R-O. +ROOH [17]
HC, CO and smoke emissions for all antioxidant mixture were
increased slightly. Further, there is no variation in BTE with the Table 1 depicts the effect of biodiesel-diesel blends on engine
addition of antioxidant additive in the biodiesel [15]. performance such as brake thermal efficiency (BTE), brake specific
fuel consumption (BSFC), exhaust gas temperature (EGT) and
The EHN is a promising antioxidant additive for controlling the NOx
exhaust emissions such as hydro carbon (HC), carbon monoxide
emission at the expense of increasing the CO and HC emissions.
(CO), oxides of nitrogen (NOx), and smoke
Further, the BHA is also capable of decreasing the NOx and HC
emission by 2.73% and 39.12% respectively at 1000 ppm
Table 1. Effect of biodiesel-diesel blends on engine performance and
concentration when compared to that of canola oil methyl ester (B20) exhaust emissions.
without additive [16]. The NOx emission for BHA and BHT
antioxidants were reduced by 9.8-12.6% when compared to that of
palm methyl ester (B20). However, the CO and HC emissions were
reduced for both antioxidants additives with B20 by 8.6-12.3% and
9.1-12.0%, respectively when compared to that of B20[17]. The NOx
emission for MENO + P200 was reduced by 35% when compared to
that of neat diesel. Further, the HC emission for MENO+P200 is
reduced by 31% at full load when compared to that of neat diesel, but
CO2, CO and smoke emissions for all concentrations were found to
be increased [18]. The NOx emission for MENO + AT100 was
reduced by 25.95% at full load when compared to that of neat
biodiesel. Further, the HC, CO and smoke emissions increases with
increasing antioxidant concentration whereas there is no significant
variation in BTE and BSFC [19]. The addition of BHT and MBEBP
antioxidants to callophyllum inophyllum (CB30) resulted reduction
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PREPARATION OF BIODIESEL BLEND Gaseous emissions data including measures of CO, CO2, NOx and
AND ANTIOXIDANT ADDITIVE HC were measured at wet sample conditions according to SAE J816B
specifications and procedures. Statistical analyses were also adopted
The P-phenylendiamine (PPDA), α-tocopherolaceate (AT) and
and measures of performance were corrected to standard atmospheric
L-ascorbic acid (LA) were selected for this present investigation
conditions (SAE J816B). Gaseous emission data included non-
because of its properties, oxidation stability, availability, cost and rate
dispersive infrared (NDIR) analysis of carbon monoxide (CO),
of suppression of NOx emission. These antioxidants were effectively
carbon dioxide (CO2) and hydrocarbons (HC) and chemiluminescent
controlling the free radical formation, since it determines the reaction
measurements of NOx and oxygen (O2). The emissions measurements
rate and prompt NOx formation in the engine. The properties of the
were done according to specifications and procedures described on
antioxidants such as PPDA, AT and LA were given in Table 4. All
SAE Engine Test Code J816b.
additives were accurately weighed for using high precision electronic
balance and added to the measured quantity of annona methyl ester.
All engine performance data were corrected to the standard
To make 50mg of antioxidant mixture 0.005%-m of antioxidant
atmospheric conditions given below.
was added to 1 kg of biodiesel. A speed mixer was used to prepare a
homogenous mixture of test fuel. The same procedure was followed
The power correction factor used was (according to Turkish
for all other test mixtures of annona methyl ester with 50 mg, 150
Standards, TS 1231).
mg, 250 mg, 350 mg and 450 mg concentrations.
Table 4. Properties of antioxidants additives[12]
where
fa =
fm=0.036qc - 1.14
qc=
Experimental Setup
The experiments were conducted on single cylinder direct injection
diesel engine which mounted rigidly on the floor as shown in Fig 1.
One end of the engine was connected with eddy current dynamometer
to apply load. The specification of the test engine as shown in Table
5. Initially, diesel fuel was filled in the tank and was supplied to the
engine through the burette. The biodiesel- diesel blend was mixed
separately kept in a small tank and supplied to the engine. The
temperature of different parts of the engine like intake, exhaust,
coolant temperature etc. were measured from the temperature sensors
on the measuring board. The U tube manometer was used to measure
the air level in the engine. The speed of the engine was measured
using the speed sensor which senses the speed of rotating crank shaft.
The smoke was measured using smoke meter. The carbon monoxide,
oxides of nitrogen and unburned hydrocarbon emissions were
measured using di-gas analyser. A computer was connected with the
engine using Data Acquisition System (a sensors interface) which
plots the graphs automatically according to the operation of the
engine. A number of tests were carried out at a constant speed of
1500 rpm and variable loads. The loads vary from no load to full
load, brake power was calculated using constant speed and the
corresponding torque. The A20 blend with various antioxidant
concentrations were used. The tests were repeated for three times and
was averaged to ensure the reproducibility of data. Uncertainty
analysis was done to prove the accuracy of experiments. The list of Figure 1. Schematic diagram of engine setup
instruments and its range, accuracy and percentage uncertainties
wereshown in Table 6.
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Table 5. The specification of the test engine 1. The experiments were conducted with A20 blend with different
concentrations of P-Pheylenediamine antioxidant additive.
2. The experiments were conducted with A20 blend with different
concentrations of α-tocopherol acetate antioxidant additive.
3. The experiments were conducted with A20 blend with different
concentrations of L-ascorbic acid antioxidant additive.
4. The experiments were conducted A20 blend with various
antioxidant additives of 250mg.
P-Phenylenediamine (PPDA)
Figure 2a shows the variation of NOx emission with brake power for
A20 blend with different concentrations of PPDA additive. The
addition of PPDA antioxidant decreases the NOx emission at all
loads. Among different concentrations, 250mg shows lower NOx
emission by 25.7% when compared to that of A20 blend at maximum
load. This is due to reduction in formation of free radicals by the
PPDA addition in the fuel. Further, the antioxidant additive PPDA has
potential antioxidant properties that trap the free radicals effectively
in the combustion chamber at all loads and hence the NOx emission
was significantly reduced. The reduction in NOx emissions increase
with the increase of concentration up to certain limit at lower
loadings and starts to decrease beyond it at higher loadings. The
possible reason for the inverse relationship between treatment
and amount of NOx reduction is that the PPDA antioxidant
contain nitrogen in its chemical structure and at higher loading,
the excess antioxidant reacts with oxygen and forms additional
NOx.[12,18]
TEST PROTOCAL
The A20 blend was selected for this present investigation and
conducted experiments to evaluate the performance and emission
characteristics of diesel engine. The antioxidant additives such as
P-Phenylendiamine, α-tocopherol acetate and L-ascorbic acid in
Figure 2a. Variation of NOx emission with brake power for A20 blend with
different concentrations of 50 mg, 150 mg, 250 mg, 350 mg and 450
different concentrations of PPDA
mg were added with A20 blend to suppress the NOx emission. The
experiments were conducted in the following manner.
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Figure 3. Variation of NOx emission with brake for A20blend with different
antioxidants (250mg)
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Figure 4. Variation of HC emission with brake power for A20 blend with Figure 6. Variation of smoke emission with brake power for A20 blend with
different antioxidants (250mg) different antioxidants (250mg)
Comparison of Carbon Monoxide Emission (CO) Comparison of Brake Thermal Efficiency (BTE)
Figure 5 shows the variation of CO emission with brake power of A20 Figure 7 shows the variation of BTE with brake power for A20 blend
blend mixed with 250 mg of different antioxidant additives. It was with 250mg of different antioxidant additives. The BTE increases
found that the CO emission decreases with BP for different antioxidant with BP for all antioxidant additives at all loads. There is a slight
additives at all loads. It was also found that the CO emission for all variation in BTE for antioxidants when compared to that of A20 at all
antioxidant additives was lower than that of A20. Among the different loads. Among the different antioxidant additives, PPDA 250mg has
antioxidant additives, PPDA 250 mg has lower CO emission than that higher BTE than that of other antioxidant additives.
of other antioxidants. This is due to reduction in carbon oxidation by
scavenging of the OH radicals and more amount of OH radicals
involved in the combustion reaction [11-12, 18-19].
Figure 7. Variation of BTE with brake power for A20 blend with different
antioxidants (250mg)
Figure 5. Variation of CO emission with brake power for A20 blend with
The reason for decrease in BTE for antioxidant additives when
different antioxidants (250mg) compared to that of A20 is due to incomplete and improper
combustion and reduction in cylinder pressure which results from the
addition of antioxidant additive in the biodiesel.
Comparison of Smoke Emission
Figure 6 shows the variation of smoke emission with brake power of
A20 blend mixed with 250 mg of different antioxidant additives. Comparison of Brake Specific Fuel Consumption (BSFC)
Figure 8 shows the variation of BSFC with brake power of A20blend
It was observed that the smoke emission increases with increasing BP mixed with 250 mg of different antioxidant additives. It was observed
for different antioxidant additives at all loads. It was also found that the from the graph that the BSFC decreases with BP for different
smoke emission was lower for all antioxidant additives than that of antioxidant additives at all loads. Among the different antioxidants,
A20. The smoke emission for PPDA was lower when compared to that PPDA shows lower BSFC than that of other antioxidants. This is due
of other antioxidant additives. This is due to complete combustion to the reduction in friction properties of the PPDA additive. The
which results from the antioxidant addition [11-12,18-19]. increase in BSFC for AT and LA is due to excess fuel supplied to the
engine and to compensate the slight power loss which results from
incomplete and improper combustion [11-12,18-19].
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APPENDIX
APPENDIX 1: THE ERROR BAR CALCULATION OF DIFFERENT ANTIOXIDANT ADDITIVES
CONCENTRATION OF 250MG WITH A20
BTE
BSFC
EGT
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CO
HC
NOx
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Smoke
APPENDIX 2
The variation of NOx for different concentration of antioxidant additive with respect to A20 blend at higher load
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