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Effect of nanoparticle additives on NOx emissions of diesel fuelled

compression ignition engine

Article  in  International Journal of Global Warming · January 2015

DOI: 10.1504/IJGW.2015.070051

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Int. J. Global Warming, Vol. 7, No. 4, 2015 487

Effect of nanoparticle additives on NOX emissions of

diesel fuelled compression ignition engine

Tayfun Ozgur*, Gökhan Tuccar,

Erinç Uludamar, Ali Can Yilmaz,
Ceyla Güngör, Mustafa Ozcanli,
Hasan Serin and Kadir Aydin
Department of Mechanical Engineering,
Cukurova University,
01330, Adana, Turkey
Email: tozgur@cu.edu.tr
Email: gtuccar@cu.edu.tr
Email: euludamar@cu.edu.tr
Email: acyılmaz@cu.edu.tr
Email: cgungor@cu.edu.tr
Email: ozcanli@cu.edu.tr
Email: hserin@cu.edu.tr
Email: kdraydin@cu.edu.tr
*Corresponding author

Abstract: The amount of emitted harmful emission gases increases in parallel

with increasing energy consumption. This increase has forced many countries
to take various precautions and various restrictions on emitted emissions have
been carried. In this study, effects of addition of oxygen containing
nanoparticle additives on NOx emissions of diesel fuelled test engine were
investigated. Nine different nanoparticle additives namely aluminium oxide
(Al2O3), magnesium oxide (MgO), titanium oxide (TiO2), zinc oxide (ZnO),
silicon oxide (SiO2), iron oxide Fe2O3, nickel oxide (NiO), nickel iron oxide
(NiFe2O4) and nickel zinc iron oxide Zn0.5Ni0.5Fe2O4 were added to diesel fuel
at the dosages of 25, 50 and 100 ppm. As a result, optimum additive and
addition dosages were determined. Finally, the results showed that NOx
emissions were decreased with the addition of nanoparticles.

Keywords: nanoparticle; nitrogen oxide; NOx; emission; additive; diesel.

Reference to this paper should be made as follows: Ozgur, T., Tuccar, G.,
Uludamar, E., Yilmaz, A.C., Güngör, C., Ozcanli, M., Serin, H. and Aydin, K.
(2015) ‘Effect of nanoparticle additives on NOx emissions of diesel fuelled
compression ignition engine’, Int. J. Global Warming, Vol. 7, No. 4,
pp.487–498.
Biographical notes: Tayfun Ozgur received his BSc degree in 2008 and
MSc degree in 2011 in the Mechanical Engineering Department of Çukurova
University, Adana, Turkey. He is currently a PhD student in the Mechanical
Engineering Department.
Gökhan Tuccar received his MSc degree in 2011 in the Mechanical
Engineering Department of Çukurova University, Adana, Turkey. He is
currently a PhD student in the Mechanical Engineering Department.

Copyright © 2015 Inderscience Enterprises Ltd.

488 T. Ozgur et al.

Erinc Uludamar received his MSc degree in 2012 in the Mechanical

Engineering Department of Çukurova University, Adana, Turkey. He is
currently a PhD student in the Mechanical Engineering Department.

Ali Can Yilmaz received his MSc degree in 2010 in the Mechanical
Engineering Department of Çukurova University, Adana, Turkey. He is
currently a PhD student in the Mechanical Engineering Department.

Ceyla Gungor received his MSc degree in 2011 in the Mechanical Engineering
Department of Çukurova University, Adana, Turkey. She is currently a PhD
student in the Mechanical Engineering Department.

Mustafa Ozcanli is an Assoc. Prof. Dr. in the Automotive Engineering

Department of Çukurova University, Adana, Turkey.

Hasan Serin is an Assist Prof. Dr. in the Automotive Engineering Department

of Çukurova University, Adana, Turkey.

Kadir Aydin is a Prof. Dr. in the Mechanical Engineering Department of

Çukurova University, Adana, Turkey.

This paper is a revised and expanded version of a paper entitled ‘Effect of

nanoparticle additives on NOx emissions of diesel fueled compression ignition
engine’ presented at the 6th International Ege Energy Symposium and
Exhibition, İzmir, Turkey, 28–30 June 2012.

1 Introduction

Urban air pollution due to vehicular emission is a matter of concern because of exposure
of large number of people to it. Vehicular emission is responsible for higher level of air
pollutants like NOx and other organic and inorganic pollutants including trace metals and
their adverse effects on human and environmental health (Barman et al., 2010). Due to
the growing concern over possible adverse health effects caused by diesel emissions, the
pollutants have been regulated by law in many developed countries (Chao et al., 2001).
Diesel engines have the advantages of better fuel economy, lower emissions of HC and
CO. However, diesel engines suffered from high emissions of PM and NOx and it is hard
to reduce them simultaneously (Yanfeng et al., 2007). To achieve substantial reductions
in emissions, it is thought that reformulated diesel fuels will play an important role. The
reformulation of diesel fuels could include lowering the sulfur content, lowering the
aromatic content, or potentially the addition of oxygen within the fuel (Ying et al., 2006).
Many researchers (Beatrice et al., 1999; Choi and Reitz, 1997; Grabowski and
McCormick, 1998; Neeft et al., 1996) concluded that many oxygenates are effective in
reducing emissions from diesel engines. In addition to this a lot of researches (Colpan
et al., 2009; Basha and Anand, 2010; Lechon et al., 2009; Panwar and Shrirame, 2009;
Pleanjai, 2009) have been conducted studies about emissions and effects of these
emissions on global warming.
Oxygenates such as dimethyl ether (DME), dimethyl carbonate (DMC), dimethoxy
methane (DMM) methanol, ethanol etc. have widely been studied. Chapman et al. (2001)
studied the effects of diesel-DME blends on engine’s emissions characteristics and their
 Effect of nanoparticle additives on NOx emissions 489

investigations showed that the emission of PM decreases with the increase of CO and
there is a small NOx reduction for some operating conditions. Bai et al. (2002) found that
DMC can reduce PM and NOx simultaneously when EGR was adopted. Maricq et al.
(1998) carried out investigations on DMM and their studies showed that the addition of
DMM causes a shift in the PM size distribution to smaller diameters and substantial PM
reduction however no change in NOx emissions. Huang et al. (2005) studied the effect of
methanol-oleic-solvent mixture on performance and emission characteristics and they
concluded that a flat NOx/smoke trade-off curve existed when the oxygenated blends
were used. Ren et al. (2008) investigated the effect of six different oxygenates on
combustion and emission of diesel engine and they reported that the smoke concentration
decreases with the increase of the oxygen mass fraction in the blends without increasing
NOx, CO and HC decrease with the increase of the oxygen mass fraction in the blends. A
flat NOx/smoke trade-off curve is presented when operating on the diesel-oxygenate
blends.
The objective of this study is to investigate the usage of nanoparticles namely MgO,
Al2O3, TiO2, ZnO, SiO2, Fe2O3, NiO, NiFe2O4 and Zn0.5Ni0.5Fe2O4 as oxygenated
additives to diesel fuel and then evaluate the characteristics of NOx emissions in a
compression ignition engine fuelled with the different proportions of nanoparticle/diesel
blends. This is a considerable step in showing that nanoparticles can give consistent,
significant results in lowering NOx emissions.

2 Material and methods

2.1 Engine and equipments

A four cylinder, four-stroke, naturally aspirated, water-cooled direct injection
compression ignition engine was used in the study. Technical specifications of test engine
were shown in Table 1. A Netfren made hydraulic dynamometer was used which has
torque range of 0–1,700 Nm and speed range of 0–7,500 rpm to measure engine torque.
Figure 1 shows the schematic representation of experimental setup. Engine performance
and exhaust emissions tests were conducted at constant speed full load condition.
Table 1 Technical specifications of the test engine

Brand Mitsubishi canter

Model 4D34-2A
Configuration In line 4
Type Direct injection diesel with glow plug
Displacement 3,907 cc
Bore 104 mm
Stroke 115 mm
Power 89 kW at 3,200 rpm
Torque 295 Nm at 1,800 rpm
Oil cooler Water cooled
Air cleaner Paper element type
Weight 325 kg
490 T. Ozgur et al.

Figure 1 Experimental equipments

Sonic Vibra-Cell VC 750 model ultrasonic processor was used to stir nanoparticles with
diesel fuel homogeneously in order to obtain blend fuels. Nanoparticles were mixed with
diesel and by pulsing time ten seconds on ten seconds off and 40% amplitude by means
of ultrasonic processor. Table 2 shows the technical specifications of ultrasonic
processor.
Table 2 Technical specifications of ultrasonic processor

Net power output 750 Watts

Power supply

Frequency 20 kHz
Dimensions: (H × W × D) 235 × 190 × 340 mm
Weight 6.8 kg
Part no. Piezoelectric lead zirconate titanate crystals
Sealed converter

Diameter 63.5 mm
Length 183 mm
Weight 900 g
Cable length 1.8 m
Tip diameter 13 mm with threaded end and replaceable tip or
solid probe with non-replaceable tip
Standart probe

Processing capability 10 ml to 250 ml

Length 136 mm
Weight 340 g
Material Titanium alloy Ti-6Al-4
 Effect of nanoparticle additives on NOx emissions 491

Testo 350 XL gas analyser was used to measure NOx emissions. Emission values were
collected with the assistance of a computer program. Measurement range of the gas
analyser for NOx emission is 0–3,000 ppm.

2.2 Nanoparticles and blends

Nine different nanoparticles were used as oxygenated additives to diesel fuel during the
experimental studies. Table 3 shows the technical specifications and cost analysis of
nanoparticles. Commercially available nanoparticles with size of 10 to 50 nanometers
were purchased for the experimental tests. The dosing levels of the nanoparticle samples
(by weight) to the base fuel were 25, 50 and 100 ppm. The required quantity of the
nanoparticle sample for each dosing level was measured with a precision electronic
balance which has a sensitivity of 0.0001 g. Diesel-nanoparticle blends were prepared in
the ultrasonic processor applying with a constant agitation time of one hour to produce a
uniform suspension.
Table 3 Properties of nanoparticles used in the experiments

Particle size Purity Cost

Nanoparticle Symbol
(nm) (%) ($/g)
Aluminum oxide Al2O3 30 99.99 0.67
Magnesium oxide MgO 30 99.9 0.48
Titanium oxide TiO2 10–50 99.99 0.76
Zinc oxide ZnO 50 99.9 0.52
Silicon oxide SiO2 < 30 99.99 0.67
Iron oxide Fe2O3 30 99.5 0.85
Nickel oxide NiO 30 99.9 0.57
Nickel iron oxide NiFe2O4 30 99.9 0.95
Nickel zinc iron oxide Zn0.5Ni0.5Fe2O4 30 99.5 0.95

3 Results and discussions

The variations of nitrogen oxides (NOx) emissions values of MgO-diesel blends versus
engine speed are shown in Figure 2. NOx emissions were reduced with the increase in the
dosage of the MgO nanoparticle additive. The maximum nitrogen oxides emission
reductions were measured as 4%, 12.3% and 37% for the blends at the nanoparticle
dosage of 25, 50 and 100 ppm respectively. The maximum nitrogen oxides emission
reduction was obtained at 2,800 rpm engine speed for the all test fuels. The average
reduction was 3.1%, 8.9% and 16.7% according to base fuel (diesel fuel) at the addition
dosage of 25, 50 and 100 ppm respectively.
492 T. Ozgur et al.

Figure 2 NOx emission values of MgO-diesel blends

1400

1200

1000
NO (ppm)
x

800

Diesel
25 ppm MgO
600 50 ppm MgO
100 ppm MgO

400
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

Figure 3 represents the variations of measured nitrogen oxides (NOx) emissions values of
SiO2-diesel blends. SiO2 addition reduced the NOx emissions by 5.4%, 13.6% and 10%
for the blends at the dosage of 25, 50 and 100 ppm respectively. The maximum NOx
emission reduction was obtained between 2,600 and 2,800 rpm engine speeds. The
average reduction was 1%, 7% and 3% in order with 25, 50 and 100 ppm SiO2 addition
respectively. Dosing level of 50 ppm SiO2 addition gave the best result for NOx
reduction.

Figure 3 NOx emission values of SiO2-diesel blends

1400

1300

1200
NO (ppm)

1100
x

1000

900
Diesel
25 ppm SiO2
800 50 ppm SiO2
100 ppm SiO2
700
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

Al2O3-diesel blends NOx variations are shown in Figure 4. The NOx emissions values of
Al2O3-diesel blends were commonly increased with the addition of Al2O3 nanoparticles.
The maximum increase ratios were 13%, 6.4% and 6.4% for the blends at the
 Effect of nanoparticle additives on NOx emissions 493

nanoparticle dosages of 25, 50 and 100 ppm respectively. The maximum nitrogen oxides
emission increase was obtained at between 2,600 and 2,400 rpm engine speeds. The
average increase was 4%, 1.4% and 0.5% compared with diesel fuel at the dosages of 25,
50 and 100 ppm respectively.

Figure 4 NOx emission values of Al2O3-diesel blends

1300

1200

1100
NO (ppm)

1000
x

900 Diesel
25 ppm Al2O3
50 ppm Al2O3
800
100 ppm Al2O3

700
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

Figure 5 shows the variations of NOx emission of ZnO-diesel blends. While addition of
25 ppm ZnO and 50 ppm ZnO decreased the NOx emissions, 100 ppm ZnO addition
increased the NOx emissions values with respect to diesel fuel. The maximum NOx
emission reduction according to diesel fuel NOx emission is 14.2% and 5.6% for 25 ppm
and 50 ppm respectively. The average reductions were 3.2% and 1% by 25 pmm and
50 ppm ZnO addition respectively. The average increase was 2.1% according to base fuel
at the addition dosage of 100 ppm.

Figure 5 NOx emission values of ZnO-diesel blends

1300

1200

1100
NO (ppm)

1000
x

900

800 Diesel
25 ppm ZnO
50 ppm ZnO
700 100 ppm ZnO

600
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

494 T. Ozgur et al.

Another reduction on NOx emissions were found with Fe2O3 nanoparticle addition. The
Fe2O3-diesel blends NOx values are shown in Figure 6. 25, 50 and 100 ppm Fe2O3
nanoparticle addition decreased the NOx emissions values of Fe2O3-diesel blend. The
maximum NOx reductions were 12.7%, 14.5% and 18.9% for 25, 50 and 100 ppm Fe2O3
additive respectively. The maximum nitrogen oxides emission reduction was obtained at
1,200 rpm engine speed for 25 ppm addition and at 2,800 rpm for 50 and 100 ppm
additions. The average reductions were 7.24%, 9.6% and 10.7% for 25, 50 and 100 ppm
dosages.

Figure 6 NOx emission values of Fe2O3-diesel blends

1600
Diesel
1500 25 ppm Fe2O3
50 ppm Fe2O3
1400 100 ppm Fe2O3

1300
NO (ppm)

1200
x

1100

1000

900

800
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

Figure 7 NOx emission values of TiO2-diesel blends

1600

Diesel
1500 25 ppm TiO2
50 ppm TiO2
1400 100 ppm TiO2
NO (ppm)

1300
x

1200

1100

1000

900
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

TiO2 nanoparticle addition to diesel fuel also decreased the NOx emissions by maximum
rates of 8.8%, 9.7% and 16.2% for 25, 50 and 100 ppm dosages respectively. Figure 7
 Effect of nanoparticle additives on NOx emissions 495

shows the variation of NOx emissions of TiO2-diesel blends. The maximum nitrogen
oxides emission reduction was obtained at 1,200, 2,800 and 1,400 engine speeds for 25,
50 and 100 ppm dosages. The average reductions were 10.2%, 6.3% and 6.9% compared
to diesel fuel in order with 25, 50 and 100 ppm.
Figure 8 shows the variations of NOx emissions of NiO-diesel blends. All ratios of
NiO addition to diesel fuel decreased the NOx emissions of NiO-diesel blends. The
maximum NOx emission reductions were 16.4%, 7.9% and 14.3% for 25, 50 and 100
ppm NiO addition respectively. The maximum NOx reduction was obtained at 2,800,
1,400 and 1,200 engine speeds for 25, 50 and 100 ppm addition amounts. The average
reductions were 8.4%, 4% and 6.5% with 25, 50 and 100 ppm NiO additions
respectively.

Figure 8 NOx emission values of NiO-diesel blends

1600

1500 Diesel
25 ppm NiO
50 ppm NiO
1400 100 ppm NiO

1300
NO (ppm)

1200
x

1100

1000

900

800
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

Figure 9 NOx emission values of Zn0.5Ni0.5Fe2O4-diesel blends

1600

Diesel
1500 25 ppm Zn0.5Ni0.5Fe2O4
50 ppm Zn0.5Ni0.5Fe2O4
1400 100 ppm Zn0.5Ni0.5Fe2O4
NO (ppm)

1300
x

1200

1100

1000

900
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

496 T. Ozgur et al.

Zn0.5Ni0.5Fe2O4-diesel blends NOx variations are shown in Figure 9. 25, 50 and 100 ppm
Zn0.5Ni0.5Fe2O4 nanoparticle addition decreased the NOx emissions of all blends. The
maximum NOx emission reductions were found 15%, 19.3% and 22.5% with 25, 50 and
100 ppm Zn0.5Ni0.5Fe2O4 addition to diesel fuel respectively. The maximum NOx
emission reduction was obtained at 1,200 engine speed for the all blends. The average
reductions were 5.1%, 9.2% and 12.6% with 25, 50 and 100 ppm respectively.
Lastly, the variations of NOx emissions of values of NiFe2O4-diesel fuel blends are
shown in Figure 10. NiFe2O4 nanoparticle addition decreased the NOx emissions with
respect to diesel fuel at all blending ratios. The maximum NOx emission reductions
against diesel fuel were found 18.7%, 19.2% and 22.1% for the blend fuels with 25, 50
and 100 ppm NiFe2O4 nanoparticle addition respectively. The maximum NOx emission
reduction was obtained at 1,200 engine speed for the all blends of NiFe2O4-diesel. The
average reductions were found 5.2%, 6.3% and 7.5% according to diesel fuel with 25, 50
and 100 ppm NiFe2O4 nanoparticle addition respectively.

Figure 10 NOx emission values of NiFe2O4-diesel blends

1600

Diesel
1500 25 ppm NiFe2O4
50 ppm NiFe2O4
100 ppm NiFe2O4
1400
NO (ppm)

1300
x

1200

1100

1000

900
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Engine Speed (rpm)

The reductions in NOx emission of diesel fuels with the additions of nanoparticles due to
the complete combustion of oxygenated fuel blends with the help of catalyst effect of
nanoparticle additions which promotes heat transfer in the combustion chamber because
of their metallic-base structures. For this purpose, combustion temperatures show a
decreasing trend which makes the peak temperatures lower in the cylinder and results
with lower NOx formations.

4 Conclusions

Nanoparticle addition to diesel fuel was investigated in order to improve the NOx
emissions of a compression ignition engine fuelled with nanoparticle-diesel blends. Nine
different oxygenated nanoparticles such as MgO, Al2O3, TiO2, ZnO, SiO2, Fe2O3, NiO,
NiFe2O4 and Zn0.5Ni0.5Fe2O4 were used during the experiments.
 Effect of nanoparticle additives on NOx emissions 497

Nitrogen oxides (NOx) emissions of diesel fuel were found to decrease with the
inclusion of the nanoparticle additives except Al2O3 nanoparticle. The maximum average
reduction was obtained with MgO nanoparticle at the addition dosage of 100 ppm as
16.7%. Nitrogen oxides (NOx) emissions of the diesel fuel were increased with the
addition of Al2O3 nanoparticle. The maximum average increase was obtained with Al2O3
nanoparticle at the addition dosage of 25 ppm as 4%. Also exhaust gas recirculation
(EGR) can be used to eliminate the NOx emissions of Al2O3 nanoparticle-diesel fuel
blends because the oxygenate fuels have high EGR tolerance due to oxygen enrichment.
With the addition of nanoparticles to diesel fuel, NOx emissions decrease significantly.
All results of oxygenated nanoparticles except aluminium-based nanoparticle indicate the
potential of diesel/nanoparticle blends for reduced NOx emission in diesel engines.

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