Fuel 182 (2016) 323332

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

Full Length Article

NOX formation of biodiesel in utility power plant boilers; Part B.

Comparison of NO between biodiesel and petrodiesel
Bahamin Bazooyar a,b, Seyed Hassan Hashemabadi b,, Ahmad Shariati a,
a
Ahvaz Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), 6198144471, Ahvaz, Iran
b
School of Chemical Engineering, Iran University of Science and Technology (IUST), 16846-13114 Tehran, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Thermal and prompt NO are obtained

from local NO concentrations.

NO for biodiesel and petrodiesel are
compared.

Increase in NO emission of biodiesel
is observed because of its high
prompt NO.

Thermal NO does not depend on the
fuel type.

Relative level of thermal and prompt
NO may be much different in the
burner.

a r t i c l e i n f o a b s t r a c t

Article history: This paper evaluates the formation of NO in a non-pressurized, water-cooled combustion chamber.
Received 5 January 2016 Thermal and prompt NO were roughly estimated from local concentrations of NO in the fumes, and were
Received in revised form 8 April 2016 studied at different burner operating points (combustion pressure, equivalence ratio, fuel spray pattern,
Accepted 5 May 2016
and swirl angle). Afterwards, thermal and prompt NO for six different methyl esters and petrodiesel were
Available online 1 June 2016
measured, compared and what mostly influences and differentiates thermal and prompt NO between
fuels was identified. Results reveal that the level of thermal NO for fuels is almost the same order of mag-
Keywords:
nitude, while prompt NO varies markedly among the fuels. The relative level of thermal and prompt NO is
NO
Thermal NO
much different depending on the operating points of the burner varying from 16/84 to up to 73/27.
Prompt NO 2016 Elsevier Ltd. All rights reserved.
Biodiesel
Petrodiesel

1. Introduction be different. To this end, the formation of NO should be unraveled

There are still many unresolved issues regarding NOX emission
of biodiesel. The most significant one is to clarify what distin-
guishes NO between biodiesel and petrodiesel and makes them
Corresponding authors.
E-mail addresses: Hashemabadi@iust.ac.ir (S.H. Hashemabadi), Shariati@put.ac.
ir (A. Shariati).
during combustion. Indeed, NO is gripped by many different fac-
tors (fuel characteristics, chemical structure [1], burner design
[2], and the combustion). Apart from combustion, what mostly
influences NO emission of fuels and probably makes them be dif-
ferent is their different properties and chemical structure. To rec-
ognize what makes NO be different, the first step is to study the
exclusive NO that comes from different mechanisms (thermal,
prompt, N2O pathway, and fuel) and to explore the influence of fuel

http://dx.doi.org/10.1016/j.fuel.2016.05.018
0016-2361/ 2016 Elsevier Ltd. All rights reserved.
324 B. Bazooyar et al. / Fuel 182 (2016) 323332

characteristics that are more pronounced in the formation of NO.
Unfortunately, exclusive determination of NO from its mechanisms
is cumbersome because these mechanisms share some commonal-
ities (e.g., dependency on temperature, pressure, and oxygen [3]).
Comparison between NO emission of biodiesel with petrodiesel
has been made by many researchers. They compared only total NO
of biodiesel and petrodiesel and assessed without any measure-
ments the thermal and prompt NO of these fuels from their char-
acteristics. Surprisingly, relative level of NO for biodiesel and
petrodiesel was obtained different. Some researches [48] reported
no significant change or slightly decrease in NO emission of biodie-
sel in comparison with petrodiesel. Others [914] observed that
biodiesel emits more NO than petrodiesel. The reasons behind
these contradictory observations are still unclear. There may be
something different in nature of biodiesel tested (i.e., fatty acid
composition, density, cetane no., and flame temperature) or differ-
ent circumstances under which the combustion occurred [15].
Whatever it is, more research needs to be done to identify those
variables that cause different NO emissions for biodiesels which
have slightly different properties, composition and circumstances
of the combustion. Despite controversial viewpoints that exist
regarding the NO emission of biodiesel, compelling reasons for
both increase and decrease of biodiesel NO are provided which
their veracity cannot be fully gainsaid nor authenticated. For

Table 1
Fatty acids composition of biodiesels (wt.%).

Structure Composition (wt.%)

(Cx:y)b SOME COME OOME GOME ROME POME
a
RA(CH2)10ACH3 C12:0 0.09
RA(CH2)12ACH3 C14:0 0.07 0.05 0.11 0.12 0.09 1.11
RA(CH2)14ACH3 C16:0 11.29 12.01 9.95 6.83 3.91 48.04
RA(CH2)6CH@CH(CH2)6ACH3 C16:1 0.17 0.04 3.41 0.65 0.11 2.08
RA(CH2)6CH@CH(CH2)7ACH3 C17:1 1.15 0.09 0.49 0.23
RA(CH2)16ACH3 C18:0 5.02 2.01 2.54 3.81 2.74 4.21
RA(CH2)7CH@CH(CH2)7ACH3 C18:1 25.37 28.04 60.15 15.56 60.51 34.41
RA(CH2)7CH@CHACH2ACH@CHA(CH2)4ACH3 C18:2T 0.13 1.28 0.05 0.41 0.59 0.56
RA(CH2)7CH@CHACH2ACH@CHA(CH2)4ACH3 C18:2CAC 51.06 53.71 21 70.22 20.14 8.25
RA(CH2)7A(CH@CHACH2)3ACH3 C18:3CAC 5.95 0.91 1.42 1.02 10.83 0.31
RA(CH2)18ACH3 C20:0 0.29 0.23 0.88 0.92 0.31 0.18
RA(CH2)8CH@CH(CH2)8ACH3 C20:1 0.36 0.34 0.46
RA(CH2)20ACH3 C22:0 0.29 0.23 0.28 0.03 0.12
RA(CH2)22ACH3 C24:0 0.12 0.25 0.41
a
R is the COOCH3 group.
b
x, number of carbons; y, number of double bonds.

Table 2
Properties of fuels.

Fuel property SOME COME OOME GOME ROME POME Petrodiesel

Fuel chemical formula C17.87H32O2 C17.84H31.97O2 C17.83H33.19O C17.95H31.51O2 C18.02H33.09O2 C17.03H32.89O2 C7H16
Stoch. air to fuel (mass basis) 12.20 12.199 12.29 12.16 12.28 12.30 13.04
Specific gravity @ 15 C 0.8821 0.8840 0.8876 0.8821 0.8895 0.8801 0.8367
Kinematic viscosity @ 40 C (cST) 5.821 5.451 5.299 5.201 5.405 5.001 3.868
Cetane number 48 47 49 46 43 68 45
Flash point (C) 171 138 167 186 179 173 44
Cloud point (C) 2 1 2 3 1 3 7
Pour point (C) 2 5 6 9 2 1 19
Gross calorific value (MJ/kg) 41.125 40.901 41.002 41.141 41.130 40.030 46.400
Fuel quality
Acid number (mg KOH/g) 0.37 0.25 0.51 0.03 0.21 0.33 0.014
Iodine number (gI/100 g) 45 44 48 41 53 50 8
Carbon residue (% m/m) 0.038 0.039 0.049 0.038 0.051 0.056 0.16
Cold filter plugging point (C) 0 3 3 1 2 2 12
Corrosion, copper strip rating 3 h @ 50 C 1a 1a 1a 1a 1a 1a 3a
Sulphated ash (% m/m) 0.008 0.009 0.006 0.004 0.005 0.003 0.012
Oxidative stability @110 C (h) 10.4 11.4 12.9 10.4 13 12.6 NA
Total contamination (mg/kg) 15 15 18 12 14 12 Trace
Water content (% w/w) 0.030 0.030 0.021 0.045 0.044 0.041 0.055
Sulfur (ppm) 1.01 1.23 1.07 1.14 0.95 1.20 435
Sodium + potassium (mg/kg) 2.45 2.31 2.89 1.15 1.89 3.89 <0.01
Calcium + magnesium (mg/kg) 0.21 0.18 0.19 0.22 0.11 0.3 0.001
Phosphorus content (mg/kg) 0.41 0.56 0.55 0.61 0.72 0.68 1.2
Methanol content (% m/m) 0.09 0.1 0.12 0.11 0.18 0.10 Trace
Linolenic acid methyl ester (% m/m) 0.51 0.09 1.04 0.54 0.99 0.14 Trace
Monoglyceride content (% m/m) 0.345 0.301 0.298 0.270 0.214 0.390 Trace
Diglyceride content (% m/m) 0.117 0.145 0.151 0.178 0.191 0.101 Trace
Triglyceride content (% m/m) 0.015 0.017 0.009 0.004 0.021 0.009 Trace
Unsaturated ME (double bond > 4) (% m/m) 0.14 0.11 0.10 0.12 0.13 0.06 Trace
Free glycerol (% m/m) 0.002 0.001 0.009 0.004 0.003 0.008 Trace
Total glycerol (% m/m) 0.118 0.125 0.137 0.139 0.112 0.136 Trace
 B. Bazooyar et al. / Fuel 182 (2016) 323332 325

instance, Tashtoush et al. [8] maintained that biodiesel emits less
NO than petrodiesel, since it contains less nitrogen. Ng and Gan
[14], in contrast, postulated that biodiesel emits more thermal
and prompt NO because of its more flame temperature, double
and triple carbonAcarbon bonds. These and other similar remarks
are all accurate and can be true. However, they are largely specu-
lative. We cannot compare NO emission of biodiesel and petrodie-
sel on such a simple ground and based on intuition from only a
property. Thermal and prompt NO both are intricate functions of
combinations of variables. A slight difference in for example a fuel
character may inversely or directly influence both thermal and
prompt NO formation, thereby making it impossible to have a reli-
able prediction about NO. In order to provide a more incisive
remarks about NO emission of biodiesel, thermal and prompt NO
should be measured and studied per se, and those fuel characters
that mostly influence their formation should be identified. This
paper steps towards this end and has the following objectives:
The first objective of this paper is to characterize thermal and
prompt NO over combustion pressure, equivalence ratio, spray pat-
tern, and combustion air swirl angle. The second objective is to
thoroughly compare the NO emission of biodiesel and petrodiesel.
The third objective is to identify compelling reasons for the differ-
ence between the NO emission of biodiesel and petrodiesel.
In non-pressurized oil burners, NO mainly forms from thermal
and prompt mechanisms [16]. Estimation of the NO that comes
from these two mechanisms can be a very big help to choose the
most felicitous NO reduction technique under different circum-
stances of the combustion because the most prevalent available
techniques are able to curtail NO from only one mechanism (either
the thermal or prompt). Unfortunately, improvements in combus-
tion quality of biodiesel accompany by increase of NOX emission
[17]. There are many novel NO reduction techniques for biodiesel
in diesel engines [1821]. The potential of these techniques in
reduction of NO at stationary combustion systems is a matter of
further investigation.
Thermal NO forms when the dissociated nitrogen reacts with
oxygen. Prompt NO, on the other hand, forms when hydrocarbon
free radicals react with nitrogen. The formation of prompt NO is
more probable at low-temperature, fuel-rich conditions, and when
the residence time of the fumes in the combustion chamber is
short. In stationary combustion systems (e.g., turbines, and boil-
ers), the contribution of prompt NO to the total NO is small. Some
authors [1,22,23] believed that slight increase of NOX in biodiesel
combustion is due to prompt NO formation.
2. Materials and method
2.1. Fuel preparation
Soybean oil (SOME), rapeseed oil (ROME), olive oil (OOME), corn
oil (COME), grape seed (GOME), and Palm oil (POME) methyl esters
were produced from transesterification of 100% pure vegetable oil
with methanol, and KOH as catalyst at optimum condition [24].

Exhaust
Air Flowmeter

Flame Temperature Probe t5

Burner Air t3 control

Testo 350z
Burner Control Box Oil Pump
+
5
5
0.7

0.2

_
5

0.50

+ 0.50
0.75
0.25

_ 3
Analysis points t2
Diffuser Fan damper
(secondary air) (primary air)

Pump Pressure Gauge

Oil Flowmeter Water Drain Valve Water

Drain Valve
Water Flow switch
t1

Condensate Drain
Cooling Water Flow Control Water Temperature Control
Oil Isolating Valve Cooling Water Drain
Oil Filter
Non-return valve
Self seal coupling
Cooling Water Flowmeter Self seal coupling

Water Isolating Valve

Priming Pump
Three-way valve

Fuel Tanks

Fig. 1. Schematic of experimental setup.

326 B. Bazooyar et al. / Fuel 182 (2016) 323332

Tables 1 and 2 give the physical characteristics and chemical struc-

ture of methyl esters and petrodiesel.

T= 1835 k
2.2. Experimental setup
32 cm

Fig. 1 depicts schematic of experimental setup used for measur-

ing level of thermal and prompt NO. It consists of a semi-industrial
boiler, and a Testo 350z gas Analyzer. The boiler is equipped with a
U.K. sterling 90 pressure jet type oil burner, water-cooled chamber,
90 instrumentation attached to the different parts of the boiler, and a
Flame monitoring system that makes the direct read-out of inlet and out-
80 let cooling water temperatures, water mass flow rates, inlet air
temperature, air flow rate, exhaust gas temperature, and fuel flow
70 Thermal NO
rate possible. More description about burner characteristics, oper-
ation of boiler, and Testo gas analyzer can be found elsewhere [16].
60

50
2.3. Operating points
40
The burner has quite steady operating points. The measure-
30
ments were recorded when the operation of the burner was at
Prompt NO steady state condition. This promises good repeatability in opera-
20
tion of the burner as well as the measurements. The level of NO
10 was measured at different operating points of the burner. Each
30 31 32 33 34 35 operating point was defined by setting the fuel combustion pres-
Air & fuel inlet Chamber lenght (cm) Rear walls
sure, primary air (022 mm), secondary air (012 mm), changing
the combustion air swirl vane (30, 37.5, 45, 52.5 and 60),
Fig. 2. Local concentration of NO. and fuel nozzle with specific spray pattern (30, 40, 60, and 90).

60 80

A B
50 70
NO emission (ppm)

40 60
NO (ppm)

30 50

20 Increase in combustion pressure 40

10 30
Increase in combustion pressure
0 20
0 500 1000 1500 2000 2500 3000 3500 0 500 1000 1500 2000 2500 3000 3500
CO emission (ppm) CO (ppm)
55 72

50
C Equivalence ratio=0.81
D
70
45
Equivalence ratio<0.81
Equivalence ratio>0.81
1
NO (ppm)

68
NO (ppm)

40

35
Equivalence ratio=0.81

30
2 1 66
Equivalence ratio>0.81

64
25

62
2
20
Equivalence ratio<0.81
15
60
0 20 40 60 80 100
0 20 40 60 80 100
CO (ppm) CO (ppm)
Prompt NO Total NO Thermal NO

Fig. 3. NO in relation to CO emission.

 B. Bazooyar et al. / Fuel 182 (2016) 323332 327

80 90

70 80

60 70

50 60
NO (ppm)

NO (ppm)
40 50

30 40

20 30

10 20
Incomplete combustion
Complete combustion
0 10
6 8 10 12 14 16 18 20 22 24 20 30 40 50 60 70 80 90 100
o
Combustion pressure (bars) Spray cone angle ( )

Thermal NO Total NO Prompt NO Thermal NO Total NO Prompt NO

Fig. 4. NO in relation to combustion pressure. Fig. 6. NO in relation to spray pattern.

comparison of NO was performed at different operating points for

80 only ROME and petrodiesel. Last, NO of petrodiesel and six methyl
Region I Region II Region III esters was evaluated and what results in different NO of fuels in
70 burners was identified. The results presented here were obtained
after a series of tests for each operating point. The uncertainty of
60 NO was calculated by propagation method of analysis [16]. The
maximum uncertainties for thermal and prompt NO are 5% and
4% respectively.
NO (ppm)

50

40
3. Results and discussion
30
3.1. Measurement of thermal and prompt NO
20
To measure thermal and prompt NO, NO was analyzed along the
10
chamber. The combustion chamber is 100 cm long. Fig. 2 shows
0.4 0.5 0.6 0.7 0.8 0.9 1.0 that 32 cm (this chamber length where the peak appeared belongs
Equivalence ratio to the optimum operating point for the combustion. For other
operating points, this length is different.) down stream of the fuel
Thermal NO Total NO Prompt NO
nozzle, NO fluctuates significantly from 19 ppm to 71.2 ppm. This
Fig. 5. NO in relation to equivalence ratio. dramatic fluctuation is likely due to the formation of thermal NO
and appearance of maximum temperature in the chamber center-
line. The timescale of thermal NO formation is few tens of
2.4. Research aims and methodology microseconds, while it is in order of nanoseconds for prompt NO
[25]. This difference in timescale gives rise to formation of thermal
First, NO was characterized during the combustion of ROME. To NO a little bit farther than prompt NO along the chamber. The
this end, thermal and prompt NO were measured and evaluated lower limit of fluctuations (19 ppm) accounts for the prompt NO
over wide range combustion pressures, equivalence ratios, spray because it forms mostly in the mixing and flame zones where
patterns, and swirl angles where the flame sustains in the burner. the hydrocarbon free radicals are prevalent, local temperatures
In the next level, NO of biodiesel and petrodiesel are compared. The are high and formation of thermal NO is limited.

Table 3
Contribution of the percent of thermal and prompt NO into total NO.

Combustion pressure (bars) 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Thermal NO (%) 16 17 18 20 21 24 26 29 30 35 42 67 71 73 73
Prompt NO (%) 84 83 82 80 79 76 74 71 70 65 58 33 29 27 27

Equivalence ratio 0.51 0.53 0.57 0.64 0.69 0.73 0.78 0.81 0.84 0.87 0.91 0.95
Thermal NO (%) 41 47 55 61 69 71 72 73 69 39 35 33
Prompt NO (%) 59 53 45 39 31 29 28 27 31 61 65 67

Spray pattern () 30 45 60 90
Thermal NO (%) 64 68 73 77
Prompt NO (%) 36 32 27 33
Swirl angle () 30 37.5 45 52.5 60
Thermal NO (%) 81 77 73 69 64
Prompt NO (%) 19 23 27 31 36
328 B. Bazooyar et al. / Fuel 182 (2016) 323332

80 sure leads to more uniform combustion (better vaporization and

propagation of fuel in the chamber [26]) and the formation of high
70 quality sprays (smaller droplet size, deep penetration of sprays in
chambers [27]). This contributes to high local temperatures and
60 disappearance of fuel local rich zones. Fig. 3 reveals an increasing
trend for thermal NO. Thermal NO highly depends on local temper-
NO (ppm)

50 atures. Increase in the combustion pressure results in high local

temperatures, therefore more thermal NO forms at complete com-
40 bustion. Prompt NO, in contrast, has an overall decreasing trend
over combustion pressure. When the combustion is of a low qual-
30 ity, local fuel rich zones appear frequently in the chamber. These
are suitable sites for prompt NO formation because prompt NO
20 highly hinges upon the concentration of hydrocarbon free radicals
[28]. At high combustion pressures (over 20 bars), when the com-
10 bustion pressure is high enough for complete combustion of what-
25 30 35 40 45 50 55 60 65
o
ever the fuel, the level of thermal and prompt NO becomes almost
Swirl angle ( ) constant 19 and 53 ppm, respectively.
Thermal NO Total NO Prompt NO

Fig. 7. NO in relation to swirl angle. 3.2.2. Equivalence ratio

Thermal NO forms mostly in the post flame, thereby highly
These two NO measured at different locations of the combus- depending on the equilibrium concentration of oxygen radicals.
tion chamber are thermal and prompt NO. Because they are func- Increase in the amount of combustion air (decrease of equivalence
tion of flame temperature and concentrations of hydrocarbon free ratio) elevates the concentration of oxygen radicals (based on
radicals (Section 3.5). established equilibrium in post flame zone O fKeq O2 g1=2
[29]), thereby promoting the formation of thermal NO (Fig. 4
3.2. Characterization of thermal and prompt NO in ROME combustion region III). Note that increase in the amount of combustion air also
has a negative influence on thermal NO. Indeed, more air in the
3.2.1. Combustion pressure chamber leads to decrease in local temperatures. Thermal NO is
Quality of the combustion in burners is largely contingent upon highly influenced by combustion temperature. Any decrease in
the combustion pressure. Indeed, increase in the combustion pres- the local temperatures leads to decrease in the level of thermal

60 60

50 50
Thermal NO (ppm)
Thermal NO (ppm)

40
40

30
30
20

20
10

0 10
6 8 10 12 14 16 18 20 22 24 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Combustion pressure (bars) Equivalence ratio

66 51

64
50
62
Thermal NO (ppm)

49
Thermal NO (ppm)

60

58 48

56 47
54
46
52
45
50

48 44
20 30 40 50 60 70 80 90 100 25 30 35 40 45 50 55 60 65
o
Spray pattern ( o ) Swirl angle ( )

Biodiesel Petrodiesel

Fig. 8. Thermal NO comparison of biodiesel and petrodiesel.

 B. Bazooyar et al. / Fuel 182 (2016) 323332 329

50 50

40 40

Prompt NO (ppm)
Prompt NO (ppm)

30 30

20 20

10 10

0 0
6 8 10 12 14 16 18 20 22 24 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Combustion pressure (bars) Equivalence ratio

30 30

25 25

Prompt NO (ppm)
Prompt NO (ppm)

20 20

15 15

10 10

5 5

0 0
20 30 40 50 60 70 80 90 100 25 30 35 40 45 50 55 60 65

Spray pattern ( )
o Swirl angle ( o )

Biodiesel Petrodiesel

Fig. 9. Prompt NO comparison of biodiesel and petrodiesel.

55.0 20

SOME
18
54.5
COME
ROME
16
54.0 GOME
OOME
14
NO (ppm)

53.5
12
53.0
10
52.5 POME
8

52.0
6
Petrodiesel

51.5 4
2141.5 2142.0 2142.5 2143.0 2143.5 2144.0 2144.5 2145.0 2145.5 0 20 40 60 80
Bis-allylic sites

Fig. 10. Thermal NO emission in relation to adiabatic flame temperature. Fig. 11. Prompt NO in relation to number of (bis-allylic sites/Avogadros number) in
each 100 moles of fuels.

NO. This gives rise to the decreasing trend of thermal NO in regions

I & II. ance of fuel local rich zones, and more prompt NO formation. There
Despite the thermal NO, prompt NO is inverse function of the is a tradeoff between these negative influences in region II, where
combustion quality. At high equivalence ratios (region III), com- prompt NO formation is very much lower.
bustion air is not enough for complete combustion of the fuel. Local
fuel rich zone appears more frequently in the chamber. As a conse- 3.2.3. Spray pattern
quence, more prompt NO forms compared with where (region II) The pattern of fuel sprayed to the chamber also varies the level
the combustion is of a high quality and local fuel rich zone disap- of thermal and prompt NO (Fig. 5). The level of thermal NO is an
pears. At low equivalence ratios (region I), the extreme flow of the increasing function of the spray pattern while, prompt NO
air to the chamber deteriorates the integrity of the flame. This also decreases as the fuel sprayed to the chamber with high cone
leads to poor distribution of fuel to the chamber, frequent appear- angles. Thermal NO formation is an equilibrium time-consuming
330 B. Bazooyar et al. / Fuel 182 (2016) 323332

ROME

70 COME 55.0
54.5
GOME
OOME
54.0
53.5
Thermal NO
68 SOME
53.0
52.5
52.0
51.5
40 45 50 55 60 65 70

NO (ppm)
66
20
18
+
16
64 14 POME
12
10 Prompt NO
8
6
62 4
40 45 50 55 60 65 70

60

58 Petrodiesel

40 45 50 55 60 65 70
Cetane No.

Fig. 12. NO emission in relation to cetane no.

54 20.0

52 19.5
Thermal NO (ppm)

Prompt NO (ppm)
50 19.0

48 18.5

46 18.0

44 17.5

42 17.0

40 16.5
0.82 0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90

72
ROME

70 COME
GOME

SOME
68
OOME
55.0
54.5
66 54.0

Thermal NO
NO (ppm)

53.5
53.0

64 52.5
52.0
POME
51.5
0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90

62 + 20
18
16
14
60 12
Prompt NO
10
8
Petrodiesel 6

58 4
0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90

56
0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90

Fig. 13. Thermal and prompt NO in relation to specific gravity.

process, thereby highly depending on residence time of the fume in and the likelihood of thermal NO formation mildly elevates. In con-
the chamber. As the fuel is widened (high spray patterns), more trast, as the flame elongated to the combustion chamber (low
time is consumed as fumes pass through the combustion chamber. spray patterns), flame loses its evenness and integrity, and as a
Consequently, residence time of the fume in the boiler increases result the level of prompt NO increases. The level of prompt NO
 B. Bazooyar et al. / Fuel 182 (2016) 323332
80
60
NO (ppm)
40
20
0 adiabatic flame temperature (to calculate flame temperature, Oli-
ROME SOME POME Petrodiesel OOME GOME
Fig. 14. Comparison of NO between methyl esters and petrodiesel.
is highest at spray pattern 30. Because of this inverse trend of
thermal and prompt NO, total NO becomes minimum at spray pat-
tern 60.
3.2.4. Swirl angle
Swirl (its velocity, angle, and penetration depth) air has a pro-
nounced role in stability of flame, quality of the combustion, and
consequently thermal and prompt NO formation. Swirl angle also
has an inverse impact upon the formation of thermal and prompt
NO (Fig. 6). The prompt NO decreases as the swirl angle increases
from 30 to 45. Increase of swirl angle indeed leads to more uni-
form mixing of the fuel and air. This contributes to increase of tem-
perature, disappearance of local fuel rich zones, and high quality in
combustion. Thus, the level of thermal NO increases as the swirl air
angle increases from 30 to 45. Increase in the combustion air
swirl angle also leads to increase in the penetration of air jet
stream. As a result, local temperature in the post flame zone
decreases. This contributes to the reduction of thermal NO at high
swirl angles because thermal NO mostly forms in the post flame.
3.3. Thermal vs. prompt: relative level
Tables 3 gives the relative level of thermal and prompt NO at
different operating points. The influence of combustion pressure
in the relative level of thermal and prompt NO is most decisive.
The contribution of thermal NO varies from 16% at 8 bars to 73%
at 22 bars. The relative level of thermal and prompt NO strongly
depends on the degree of completion of the combustion. When
the combustion is of a high quality, thermal NO accounts for
majority of NO emission. Thermal NO is direct function of combus-
tion quality, while prompt NO is an inverse function of the com-
bustion quality. Total NO is a linear function of CO (Fig. 7).
3.4. Comparison of biodiesel and petrodiesel NO
Fig. 8 gives the trend of thermal NO for ROME and petrodiesel
over different burner operating points. It reveals the overall same
behavior of thermal NO for fuels. It can be readily seen from the
graph that thermal NO for petrodiesel is slightly higher than or
even comparable with that for ROME. Indeed, the formation of
thermal NO depends on many different variables such as: availabil-
ity of oxygen, local temperatures, and residence time. Note that at
some operating points, biodiesel emits more prompt NO that pet-
rodiesel (equivalence ratio = 0.8, spray pattern = 60). Prompt NO
for ROME and petrodiesel is compared in Fig. 9. Despite thermal
NO which is comparable for fuels, prompt NO forms noticeably
more in the combustion of ROME than in combustion of petrodie-
331
sel. Prompt NO is largely influenced by concentration of free
hydrocarbons. The discrepancy between prompt NO of fuels shows
that hydrocarbons in ROME combustion are more widespread than
in petrodiesel combustion. This is likely resulted from number of
bis-allylic sites ROME that is higher than that for petrodiesel.
3.5. Different NO emission of biodiesel and petrodiesel: main reasons
The influence of biodiesel characteristics in the formation of NO
was previously authenticated [22]. Fig. 10 shows thermal NO is dif-
ferent depending on flame temperature for the fuels. Like in diesel
engines [30], thermal NO is an exponential function of flame tem-
perature (low argument of exponential function is a linear function
at low variations). Thermal NO perfectly correlates in a line with
COME kara and Borman [31] FORTRAN codes were used. Lapuerta Gaus-
sian method [32] was used for determination of methyl esters
enthalpy of formation). Adiabatic flame temperature is an intrinsic
fuel property that mainly depends on enthalpy of formation, carbon
chain length, and number and position of double bonds. Thus, what
differentiates thermal NO among fuels is a combination of these
characteristics that appears with their adiabatic flame temperature.
Prompt NO, on the other hand, mainly depends on the concentra-
tions of hydrocarbon free radicals. The concentration of hydrocar-
bon free radicals is a direct function of numbers of bis-allylic sites
(methylene CH2 directly adjacent to the two double bonds) [33].
Fig. 11 shows that prompt NO approximately matches the number
of bis-allylic sites. Among fuels, petrodiesel has the lowest number
of bis-allylic sites and prompt NO. ROME in contrast, emits the
highest prompt NO. Prompt NO for other methyl esters located
between those for ROME and petrodiesel. Thus, what makes the
prompt NO for the fuels be different is their different numbers of
bis-allylic sites. Fig. 12 gives the level of NO in relation to the cetane
number of fuels. Although NO for methyl esters shows some tidi-
ness in relation to the cetane number, cetane number is not main
reason of difference in NO emission of biodiesel and petrodiesel
(NO for petrodiesel does not perfectly match the trend of methyl
esters). Likewise, different density of methyl esters and petrodiesel
does not give rise to their different NO emission. Note that the level
of NO for the fuels with high densities is more than that for low
dense fuels (Fig. 13). However, the difference among the NO emis-
sion of fuels is far greater than it can be attributed to difference in
density. The small figure on top of Fig. 13 shows the level of thermal
and prompt NO in relation to density of ROME when its density var-
ies in the range of densities in figure on down. The variation of NO
emission for ROME in relation to density is far less than that for
fuels with the same range of density. Thus, density of a fuel cannot
be a strong reason for its different NO emission with another fuel.
Fig. 14 shows the relative level of NO for the fuels at their optimum
combustion conditions. It shows that all methyl esters emit more
NO (thermal + prompt) than petrodiesel. However, as was depicted
in Figs. 8 and 9 biodiesel may emit similar or even lower both ther-
mal and prompt NO at some burner operating points. As a conse-
quence, beside fuel characteristics, what may also differentiate
the level of NO emission among the fuels can be the circumstances
under which the combustion occurs.
4. Conclusions
The main following conclusions are obtained:
I. The relative level of thermal and prompt NO and their con-
tribution to the total NO are different over burner operating
points depending on the degree of completion and quality of
the combustion.
332 B. Bazooyar et al. / Fuel 182 (2016) 323332
II. Thermal and prompt NO become almost constant at 19 bars.
Thermal and prompt NO possess a maximum and a mini-
mum at equivalence ratio 0.81, respectively.
III. Thermal and prompt NO inversely vary in relation to the
spray pattern and swirl angle.
IV. What mostly influences and may distinguishes the NO
between the fuels is their adiabatic flame temperature and
number of bis-allylic sites. Adiabatic flame temperature of
fuels perfectly matches their thermal NO. Prompt NO has a
semi-direct relationship with number of bis-allylic sites.
V. Methyl esters emit more NO than petrodiesel at their opti-
mum combustion conditions.
VI. Thermal NO for all fuels is very much close to each other and
is independent on the type of the fuel (based on the uncer-
tainty of experiments). The difference between NO emission
of fuels is mostly because of their different prompt NO.
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