Fuel 255 (2019) 115854

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Fuel
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Full Length Article

Simultaneous reduction of NOx and smoke emissions with low viscous T

biofuel in low heat rejection engine using selective catalytic reduction
technique
⁎
V. Karthickeyana, S. Thiyagarajanb, , V. Edwin Geob, B. Ashokc, K. Nanthagopalc,
Ong Hwai Chyuand, R. Vigneshc
a
Department of Mechanical Engineering, Sri Krishna College of Engineering and Technology, Coimbatore, India
b
Green Vehicle Technology Research Centre, Department of Automobile Engineering, SRM Institute of Science and Technology, Kattankulathur, India
c
School of Mechanical Engineering, Vellore Institute of Technology, Vellore, India
d
Department of Mechanical Engineering, University of Malaya, Malaysia

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: The present work offered a comprehensive investigation on engine characteristics of single cylinder Direct
Biofuel Injection (DI) diesel engine fuelled with Lemon oil (LO) biofuel. LO was obtained from the peels of lemon using
Cetane enhancer steam distillation process. The physio-chemical properties of LO were analysed based ASTM biodiesel standard
Thermal barrier coating and compared with diesel. The chemical composition of LO was observed with Fourier Transform Infrared
NOx emission
Spectroscopy (FTIR) and Gas Chromatography and Mass Spectrometry (GC–MS). In-order to enhance the
SCR
Smoke emission
properties of LO, a cetane enhancer namely Pyrogallol (PY) was added. The engine combustion chamber
components namely piston head, cylinder head and intake and exhaust valves were thermally coated with
Partially Stabilized Zirconia (PSZ) which converted the conventional engine into low heat rejection engine. In
the PSZ coated engine, enhanced performance and combustion characteristics were observed with LO and PY
blend. Declined carbon monoxide (CO), hydrocarbon (HC) and smoke emissions were observed with LO and PY
blend in coated engine. Further, the work was extended with the application of Selective catalytic reduction
(SCR) and Catalytic Converter (CC) as post treatment system for the reduction of NOx emission. With post
treatment, LO and pyrogallol in PSZ coated engine showed lower NOx emission than diesel and LO.
Consequently, LO and pyrogallol in PSZ coated engine with post treatment was considered as more advantageous
than other fuel samples on account of its performance, combustion and emission characteristics.

⁎
Corresponding author.
E-mail address: thiyagas@srmist.edu.in (S. Thiyagarajan).

https://doi.org/10.1016/j.fuel.2019.115854
Received 14 January 2019; Received in revised form 3 July 2019; Accepted 21 July 2019
Available online 24 July 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Nomenclature HRR Heat Release Rate (kJ/m3deg)

ICP In-Cylinder Pressure (bar)
ASTM American Standards for Testing and Materials LO Lemon Oil biofuel
BTE Brake Thermal Efficiency (%) LO + A Lemon oil biofuel with Cetane enhancer
BSCO Brake Specific Carbon Monoxide (g/kWh) LO + C Lemon oil biofuel with Thermal Barrier Coating
BSFC Brake Specific Fuel Consumption (g/kWh) LO + A + C Lemon oil biofuel with Cetane enhancer and Thermal
BSNOx Brake Specific Oxides Of Nitrogen (g/kWh) Barrier Coating
BSHC Brake Specific Hydrocarbon (g/kWh) LO + A + C + PT Lemon oil biofuel with Cetane enhancer,
CI Compression Ignition Thermal Barrier Coating and Post Treatment system
CC Catalytic Converter NOx Oxides of Nitrogen (ppm)
CO Carbon monoxide (% volume) PT Post Treatment
DI Direct Injection PY Pyrogallol
FTIR Fourier Transform Infrared Spectroscopy PSZ Partially Stabilized Zirconia
GC–MS Gas Chromatography–Mass Spectroscopy SCR Selective Catalytic Reduction
HC Hydrocarbon (ppm) TBC Thermal Barrier Coating

1. Introduction
Owing to advanced thermal efficiency, low cost, operational con-
sistency and stability, diesel engine was said to be appropriate for
heavy-duty applications, transportation, industry sectors compared
with their gasoline equivalents. Regardless of these benefits, diesel
engine incurred the problem of discharging harmful pollutants like CO,
HC, NOx and smoke emissions. Thus, heavy usage of diesel in trans-
portation and manufacturing sectors and the following environmental
issues such as global warming and greenhouse effect have stimulated
attention to replace this fuel with its renewable alternative, i.e., bio-
diesel/biofuel. As biofuels exhibited similar physiochemical properties
as like diesel, it may be used in diesel engines with engine modification
techniques. In order to achieve better performance, combustion and
emission characteristics, many strategies like addition of Cetane en-
hancer, Thermal Barrier Coating and Post treatment systems (Selective
Catalytic Reduction and Catalytic Converter) were attempted in the
experimentation.
1.1. Low viscous biofuel
Biofuels were characterized by its physiochemical properties like
low viscosity and enhanced calorific value which offers better fuel
atomization and better evaporation. Furthermore, the heating values of
biofuels were virtually equal to mineral diesel. Nowadays, the research
on biofuels have gained the consideration to substitute the diesel with
the eco-friendly alternatives. Turpentine oil was one of the biofuel
produced by pyrolysis method or from resins of pine tree dissolved in
volatile liquid [1]. Turpentine oil was blended with diesel at various
proportions and investigated in DI diesel engine. Increased fuel con-
sumption and decreased thermal efficiency were noticed with turpen-
tine oil blends due to low calorific value and marginal kinematic visc-
osity. Lower smoke and particulate matter emission was noticed with
turpentine oil than diesel. Similarly, pine oil was also considered as the
prime low viscous biofuel obtained from resins of pine tree [2]. Engine
studies revealed that the pine oil and its blends exhibited better per-
formance, combustion and emission characteristics than diesel with the
exception of NOx emission. Similar results were obtained with pine oil
biofuel in diesel engine by fumigation in the engine intake manifold [3]
and investigation of pine oil and its blends in Kirloskar TAF1 CI engine
[4]. Cymbopogon flexuosus or lemon grass oil was produced using steam
distillation process [5]. Biofuel blends showed lower thermal efficiency
and higher fuel consumption than diesel. Also, combustion character-
istics found to diminish with high NOx emission. But other emissions

Table 1
Comparison of engine performance, combustion and emission characteristics of diesel and biofuels.
Research group and Biofuel source and samples Test engine specification Performance Emission Combustion Outcomes Ref.
year

Anand et al. (2010) Turpentine oil biofuel (TPOF), Kirloskar TV1, 4S, DI, CI, CR BTE ▾ Smoke ▾ HRR ▲ - 70:30 DF/TPOF exhibited high brake [1]
50:50 DF/TPOF, 60:40 DF/ 17.5:1, RS 1500 rpm, RO SFC ▲ PM ▾ ICP ▲ power and HRR
TPOF and 70:30 DF/TPOF 5.2 kW, IP 220 bar, IT 23° - In fuel injector tip, no carbon deposit
bTDC observed
Vallinayagam et al. Pine oil 25% pine oil, 50% Kirloskar, 4S, DI, CI, CR BTE ▲ CO ▾ ICP ▲ - All engine characteristics found suitable [2]
(2013) pine oil, 75% pine oil and 17.5:1, RS 1500 rpm, RO BSFC ▾ HC ▾ HRR ▲ except NOx and can be controlled using
100% pine oil 5.2 kW, IP 220 bar, IT 23° NOx ▲ various engine modification techniques.
bTDC, WC Smoke ▾
Vallinayagam et al. Pine oil (PO) fumigation Kirloskar, 4S, DI, CI, CR – CO ▾ – - Injection of pine oil in intake manifold [3]
(2014) 0.0291 g/s PO, 0.0873 g/s 17.5:1, RS 1500 rpm, RO HC ▾ can be controlled by electronic system
PO, 0.13968 g/s PO 5.2 kW, IP 220 bar, IT 23° NOx ▲ may control NOx emission.
bTDC, WC Smoke ▾
Dhinesh et al. Cymbopogon flexuosus biofuel Kirloskar TV1, 4S, DI, CI, CR BTE ▾ CO ▾ ICP ▾ - C20-D80 biofuel blend may be [5]
(2016) C10-D90, C20-D80, C30-D70, 17.5:1, RS 1500 rpm, RO BSEC ▲ HC ▾ HRR ▾ considered as effective alternative fuel.
C40-D60 and C100 5.2 kW, IP 200 bar, IT 23° NOx ▲
bTDC Smoke ▾

DF- Diesel fuel, 4S- Four stroke, DI- Direct injection, CI- Compression ignition, CR- Compression ratio, RS- Rated speed, RO- Rated output, IP- Injection pressure, IT-
Injection timing, bTDC- before Top Dead Centre, BTE- Brake thermal efficiency, SFC- Specific fuel consumption, PM- Particulate matters, HRR- Heat release rate, ICP-
In-cylinder pressure, WC- Water cooled, BSFC- Brake specific fuel consumption, CO- Carbon monoxide, HC- Hydrocarbon, NOx- Oxides of nitrogen, 1C- Single
cylinder, BSEC- Brake specific energy consumption.

2
V. Karthickeyan, et al.
like CO, HC and smoke were decreased due to high combustion
chamber temperature. Waste lemon and its peels were used as the
prime source for biofuel production. Lemon oil biofuel was obtained
using steam distillation process and blended with diesel under volu-
metric proportions [6]. Due to presence of oxygen content in fuel and
increased combustion chamber temperature, lemon oil and its blends
showed high NOx emission. Lemon oil was converted into emulsified
fuel for application in single cylinder direct injection diesel engine [7].
Water, Span 80 and Methyl-dihydroxy propyl imidazolium were used
for the preparation of emulsified fuel with lemon oil biofuel. A trivial
enhancement in thermal efficiency was observed with emulsified fuel
than other fuel samples. A notable decline in NOx and smoke emission
was perceived with emulsified fuel. 20% of lemon oil biofuel with 80%
diesel was investigated in Kirloskar single cylinder direct injection
diesel with various injection pressures (400, 500 and 600 bar) and 10%
of biofuel as pilot fuel injection with and without exhaust gas re-
circulation [8]. Operation of fuel blends at various injection strategies
showed satisfactory results with expense of NOx emission. Table 1
presents the comparison of engine performance, combustion and
emission characteristics of diesel and biofuels.
1.2. Engine modification techniques to improve performance, combustion
and emission characteristics
Though biofuel was low viscous fuel, it incurred lower cetane index
than diesel. Thus, the addition of cetane enhancer to biofuel was said to
be promising technique to achieve improved quality of fuel. Orange oil
biofuel was obtained by steam distillation method and investigated in
DI diesel engine [9]. To improve the combustion characteristics, 36 mg/
s of di-ethyl ether was introduced at engine intake manifold along with
orange oil biofuel. Orange oil with DEE experienced better performance
and combustion characteristics than diesel. Lower NOx was observed
with the expense of other emissions like CO, HC and smoke. Ignition
promoters namely iso-amyl nitrate and di-tertiary ignition promoter
blends butyl peroxide were blended separately with pine oil-diesel
blend and investigated in DI diesel engine [10]. Improved thermal ef-
ficiency and decreased fuel consumption was noticed with ignition
promoter blend due to change in properties of fuel. At all loads, pine oil
blends showed lower CO and smoke emissions (Except NOx and HC
emissions) than diesel. Lemongrass oil blend (namely 25% biofuel with
75% diesel) was examined with two antioxidants (namely butylated
hydroxyanisole and butylated hydroxytoluene) under various con-
centrations (500, 1000 and 2000 ppm by weight) in DI diesel engine at
various loads [11]. Lemongrass oil and antioxidant blend showed better
performance and emission characteristics than neat diesel. Energy
Fig. 1. Steam distillation method for lemon oil production.
3
Fuel 255 (2019) 115854
supervision and efficacy have been the issue for engineers dealing with
Internal Combustion Engines. Diesel engine discards nearly two-third of
heat energy of the fuel, one-third toward the coolant, and one third as
the exhaust, leaving almost one-third as the beneficial power output.
Therefore, the decrease in heat rejection provides the way for en-
hancement in the thermal efficiency. In diesel engine, the combustion
chamber walls were thermally coated by ceramics was referred to as
Low Heat Rejection (LHR) engine. Cashew nut shell liquid was in-
vestigated in conventional and Partially stabilized zirconia coated
diesel engine and compared with diesel [12]. In coated engine, cashew
nut shell oil showed higher ICP than diesel due to oxygen content in
fuel and enhanced combustion chamber temperature. Due to TBC and
improved fuel properties, cashew nut shell oil showed high thermal
efficiency and low fuel consumption. PSZ coated engine showed lower
CO, HC and smoke emissions (except NOx) than uncoated engine. Si-
milarly, cotton seed oil- diesel blends with zirconium oxide coating was
investigated in DI Rainbow 186 diesel engine [13]. Improved engine
torque and power were noticed with cotton seed oil- diesel blend in
coated engine than diesel fuel. Zirconium oxide coated engine showed
lower CO, HC and smoke emissions (except NOx) than uncoated engine.
In order to reduce NOx emission, Post treatment (PT) system was at-
tempted in the present work. PT includes Selective catalytic reduction
(SCR) and Catalytic converter (CC) setup. SCR and CC technology was
said to be the promising technology to achieve declined engine exhaust
emission particularly NOx. Neat diesel and pine oil blend was in-
vestigated in DI diesel engine with SCR and CC [14]. Reduced exhaust
emission was noticed with pine oil and its blends in SCR and CC engine
than conventional engine. Neem oil biodiesel- diesel blends were in-
vestigated in diesel engine with aqueous urea base SCR and monolith
catalytic converter to obtain reduced engine exhaust emissions [15].
From the above cited literatures, it has been identified that the fuel
scarcity and environmental emissions were the major problems glob-
ally. Biofuel was considered as one of the prime source for application
in automotive and power generation with reduced emission char-
acteristics. In recent years, new biofuels were explored from various
non-edible plant based oils for application in diesel engine. In the
present work, the biofuel from lemon peel was considered as the source
of attention due to its abundant availability and preferring physical and
chemical properties like low kinematic viscosity and boiling point.
Furthermore in the technical literature so far, the application of lemon
peel oil in CI engine showed better performance with penalty of NOx
and smoke emission in the exhaust. Within this context, the present
research work focussed on the development of strategy towards the
simultaneous reduction of NOx and smoke emission without compro-
mising the thermal efficiency. From the literature review, limited
V. Karthickeyan, et al. Fuel 255 (2019) 115854

experimental works were witnessed based on the impact of antioxidant, ramp temperature increments. Initially, 10 °C per minute was used to
thermal barrier coating and post treatment systems (SCR and CC) on obtain the final temperature of 150 °C and 2 min was provided as
engine characteristics of a low viscous bio-fuelled diesel engine. Hence, holding time. Followed by, the second ramp was initiated with 5 °C per
the aim of the present work was to investigate the combined effect of minute to obtain final temperature of 220 °C and 1 min was used as
cetane enhancer, TBC and post treatment system (SCR and CC) on en- holding time. The last ramp was started with 10 °C per minute to obtain
gine characteristics of single cylinder diesel engine fuelled with Lemon the programmed temperature of 260 °C and last 10 min was provided as
oil biofuel. holding time. The preparation run timeout was observed as 20 min with
equilibrium time of 0.5 min. In the splitless mode condition, 1 micro
2. Materials and methods litre of sample was injected at the final temperature of 260 °C. The
obtained mass spectra values were evaluated and compared with the
The present research work includes the various stages such as fuel available references in NIST and WILEYS mass spectra library [16]. The
preparation, fuel properties assessment and fuel blend preparation with chemical components in lemon oil were presented in Table 3. From
Cetane enhancer. The following sections discuss the detailed process of GC–MS analysis, the presence of trans-isolimonene (C10H16) with peak
fuel preparation and its properties characterization process. area of 84.66% was observed in the extended chromatogram. Other
components like pinene and terpinene were observed at various peak
2.1. Fuel production positions. Limonene (C10H16) accounts for 84.66% of the total fatty
acids. Fig. 3 represents the GC–MS results LO biofuel. From the GC–MS
Fig. 1 depicts the steam distillation method for lemon oil produc- analysis, the presence of limonene in LO makes it to be the feasible
tion. Lemon oil production was carried out by using steam distillation alternative to conventional fuel. Due to the presence of limonene, the
process under controlled operating parameters. A small scale produc- characteristics of lemon peels didn’t change with the samples obtained
tion unit with three different operating capacity of 80, 90 and 100 kg of from different times.
waste lemon peels was used for oil production. Waste lemon peels were
collected for three consecutive days and stored in air tight container. 2.3. Fuel property analysis
Dried lemon peels were chopped into small pieces and filled in the
chamber. The bottom of the chamber was attached to the steam boiler The fuel properties like density, kinematic viscosity and flash point
outlet where steam passed into the chamber. Boiler was operated and and fire point were determined based on ASTM D1298, D445 and D93
the steam was allowed inside the chamber at different flow rates of 13, standard testing procedure respectively [17,18]. Pensky Martin closed
14 and 15 L per hour and the fumes were collected inside the con- cup fire point apparatus was used to determine the flash point and fire
denser. Water was circulated continuously for condensation process. point of lemon oil. Kinematic viscosity was determined by using Red-
The last obtained solution was collected in a beaker and observed that wood viscometer apparatus. In compression ignition engine, ignition of
the floral water settled at the bottom and lemon oil rises to the top due fuel was considered as one of the important factor as it directly influ-
to variation in density. Lemon oil with some impurities was separated ences the emission characteristics of fuel. Therefore, calorific value was
and few proportion of ether was added. Lemon oil was heated for few determined by using bomb calorimeter apparatus. Table 4 shows the
minutes to remove the water vapour and volatile substance. To remove comparison of physical and chemical properties of diesel, orange oil
the impurities, lemon oil was filtered with filter paper and last derived and lemon oil.
oil was termed as neat lemon oil. After 3 h, maximum yield of oil was
observed as 560 ml for 100 kg waste lemon peels at steam flow rate of 2.4. Role of cetane enhancer
15 L per hour.
From the physical and chemical properties analysis, it was observed
2.2. FTIR and GC–MS analysis that the cetane number of lemon oil was lower than diesel and orange
oil. To improve the cetane number, cetane enhancers might be added
FTIR and GC–MS analyses were carried out in SITRA (South Indian with testing fuel. Some of the cetane enhancers available in market
Textile Research Associate), Coimbatore. FTIR analysis was carried out were 1-pentanol, 1-butanol, iso-amyl nitrate, di-tertiary butyl peroxide,
in Thermo Scientific make Nicolet IS 10 model machine. The spectrum pyrogallol (PY) and the like. Addition of an additive with fuel helps to
was recorded between 3995.85 and 455.13 cm−1. For entire testing, the improve the flow properties, pour point and cetane number. In the
total number of background scan and sample scan were fixed as 32. present investigation, 1% of Pyrogallol (C6H6O3) solution was added
Table 2 shows the FTIR analysis results. The presence of alcohol group with lemon oil and stirred continuously for 15 min using hot plate
was identified in 3592.74 and 3564.92 cm−1 with OeH bond group and
stretch vibration. The carboxyl components were identified at 1789.75 Table 2
and 1681.85 cm−1 with C]O bond group and stretch vibration. Pre- FTIR analysis result.
sence of aromatics and amines were observed at 1435.62 and Characteristic absorptions Function group Bond type Type of
1147.10 cm−1 with stretch vibration. Absorptions at 3070.87, 2965.72, (cm−1) operation
2912.51, 1644.42, 1376.25, 914.03, 886.56 and 797.58 cm−1 were
identified as alkene functional group. The absorption peak at 3592.74 Alcohol OeH Stretch, free
3564.92 Alcohol OeH Stretch, free
2249.21 cm−1 showed the presence of alkyne functional group with
3070.87 Alkene ]CeH Stretch
stretch vibration. Fig. 2 shows the FTIR result of lemon oil. 2965.72 Alkane CeH Stretch
GC–MS analysis was carried out using Thermo GC–MS Trace Ultra 2912.51 Alkane CeH Stretch
equipment (version 5.0) with data acquisition system (version II). DB 2249.21 Alkyne eC]Ce Stretch
1789.75 Carbonyl C]O Stretch
35 model MS capillary non-polar standard column with dimensions of
1681.85 Carbonyl C]O Stretch
30 m × 0.25 mm (ID) and a film thickness of 0.25 μm was used. Pure 1644.42 Alkene C]C Stretch
helium of 99.999995% was used as a carrier gas with a flow rate of 1435.62 Aromatic C]C Stretch
1.0 ml/minute. The mass spectroscopy of mass electron was fixed from 1376.25 Alkane eCeH Bending
lower mass of 50 m/z to higher mass of 650 m/z with 70 eV as ioni- 1147.10 Amines CeH Stretch
914.03 Alkene ]CeH Bending
zation energy. The oven was programmed to operate at temperature
886.56 Alkene ]CeH Bending
initiating from 70 °C to reach 260 °C at an average increment of 6 °C per 797.58 Alkene ]CeH Bending
minute. Initial to final temperature attainment was depicted as three

4
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Fig. 2. FTIR result of lemon oil biofuel.

Table 3
Components identified using GC–MS.
S.No. Compound Name Probability Molecular Formula Molecular Weight Area %

1. à-PINENE, (−)- 28.79 C10H16 136 1.36

2. ç-Terpinene 10.05 C10H16 136 7.70
3. 2-á-PINENE 17.83 C10H16 136 0.05
4. TRANS-ISOLIMONENE 10.99 C10H16 136 84.66
5. à-Terpinene 20.91 C10H16 136 2.75
6. 2,4,6-Octatriene, 2,6-dimethyl- 10.80 C10H16 136 0.14
7. 5-Caranol, trans,trans-(+)- (CAS) 9.10 C10H18O 154 0.23
8. Cyclopentaneacetaldehyde, 2-formyl-3-methyl-à-methylene-(CAS) 6.46 C10H14O2 166 0.01
9. à-TERPINENYL ACETATE 19.70 C12H20O2 196 0.14
10. Carane, 4,5-epoxy-, (E)- 10.75 C10H16O 152 0.03
11. Z-Citral 42.09 C10H16O 152 0.69
12. Citral 27.06 C10H16O 152 0.87
13. 1,4-dihydroxy-p-menth-2-ene 21.45 C10H18O2 170 0.01
14. O-NEO-ISOMENTHYL ACETATE 7.90 C12H22O2 198 0.01
15. NERYL ACETATE 21.85 C12H20O2 196 0.13
16. Geranyl acetate 16.98 C12H20O2 196 0.05
17. (−)-á-Elemene 11.07 C15H24 204 0.01
18. trans-Caryophyllene 8.14 C15H24 204 0.13
19. à-Cubebene 4.29 C15H24 204 0.01
20. Valencene (CAS) 7.25 C15H24 204 0.10
21. ë-Cadinene (CAS) 15.09 C15H24 204 0.02
22. 1H-Benzocycloheptene, 2,4a,5,6,7,8,9,9a-octahydro-3,5,5-trimethyl-9-methylene-, (4aS-cis)- (CAS) 12.60 C15H24 204 0.85
23. Hedycaryol 16.15 C15H26O 222 0.01
24. DIEPI-à-CEDRENEPOXIDE 28.48 C15H24O 220 0.02
25. à-Ylangene 11.30 C15H24 204 0.01
26. 5á,7áH,10à-Eudesm-11-en-1à-ol 10.51 C15H26O 222 0.01
27. Longipinocarveol, trans- 13.00 C15H24O 220 0.01

magnetic stirrer to obtain homogeneous testing sample. No phase se-
paration was identified by visual inspection after 6 h of stirring op-
eration. Also, it was reported that the pyrogallol helps in maintaining
the same kinematic viscosity after long storage period compared to
other additives [19]. PY was an organic component which helps in
homolysis during combustion of fuel. Table 5 shows the properties of
Pyrogallol.
2.5. Role of thermal barrier coating
In diesel engine, many researchers have attempted engine mod-
ification techniques like thermal barrier coating, exhaust gas re-
circulation, combustion chamber bowl geometry modification and so
forth to achieve improved performance and reduced exhaust emission
characteristics. The present study focussed on thermal barrier coating
technique to obtain reduced heat transfer from combustion chamber to
engine cooling water jacket. This trapped heat was used to improve the
engine combustion characteristics directly. The process of insulating

5
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Fig. 3. GC–MS chromatogram of lemon oil biofuel.

Table 4 combustion chamber walls by ceramic materials is said to be Low Heat

Physical and chemical properties of diesel and lemon oil. Rejection (LHR) engine [20,21]. Combustion chamber components like
Properties Diesel Lemon oil Orange oil Limits ASTM
cylinder head, piston head and intake and exhaust valves were coated
[9] standards with ceramic coating material namely partially stabilized zirconia
(PSZ). The composition of PSZ includes 8 mol% of MgO, 8 mol% of CaO
Density (kg/m3)* 835.1 848.57 816.9 880 D1298 or 3 to 4 mol% of Y2O3. PSZ was used as a coating material due to high
Kinematic viscosity 2.57 1.02 3.52 1.9–6.0 D445
at 40 °C (cSt)*
coefficient of thermal expansion and low thermal conductivity. Gen-
Flash point (°C)* 56 48 74 130 Min. D93 erally, cracks were possible in the coating layer at high combustion
Fire point (°C)* 62 54 82 – D93 temperature whereas the tetragonal phase of PSZ can withstand high
Gross calorific value 43.26 42.76 34.65 – D240 temperature and control the crack formation. Selected engine com-
(MJ/kg)*
bustion chamber components were micro-grained to reduce by 500 μm
Calculated cetane 48 12 47 47 Min. D613
number for coating purpose. Then, the components were ultrasonically cleaned
C (mass %) 86.6 88.62 – – – with anhydrous ethylene glycol solution to remove suspended particles
H (mass %) 13.39 9.87 – – – and allowed to dry in atmospheric temperature.
O (mass %) – 1.51 – – – Table 6 shows the operating condition of plasma spray coating
technique. In the present study, the air plasma spray coating technique
* All properties were identified based on ASTM standards under laboratory
condition. was used for ceramic coating. Initially, spray booth cylinder head was
fixed in the chuck and tighten with accessories. The spray gun and
cylinder head surface was fixed at a distance of 90 to 100 mm under
Table 5
Properties of Pyrogallol. optimized operating condition. Machine operating parameters like
voltage and current were fixed as 60 to 70 V and 575 to 600 A re-
Property PY spectively. 100 μm of lining ceramic material namely NiCrAl was ap-
Molecular structure plied on the surface to improve the bonding between surfaces and
coating material. Argon gas was used as a carrier gas and the material

Table 6
Operating condition for plasma spray coating machine.
Molecular formula C6H6O3 Machine Parameters Bond coat (NiCrAl) TBC (PSZ)
Chemical name Benzene-1,2,3- triol
Molecular weight (g/mol) 126.11 Voltage (V) 60 70
Density (g/cm3) 1.45 Current (A) 575 600
Flash point (°C) 230 Argon gas flow rate from plasma gun (l/min) 30 35
Boiling point (°C) 309 Nitrogen gas flow rate from plasma gun (l/ 5 7
min)
Torch distance from material surface (mm) 100 90
Material feed rate (g/min) 60 40

6
V. Karthickeyan, et al. Fuel 255 (2019) 115854

was allowed to pass on the high temperature zone in the gun and ac-
celerated at high velocity and settles at the substrate. In plasma gun,
argon and nitrogen flow rate were fixed as 30–35 lpm and 5–7 lpm
respectively. The plasma spray coating machine material feed rate was
fixed between 40 and 60 g/min. Followed by, 100 μm of PSZ was ap-
plied and left undisturbed for some time. Then, similar coating proce-
dure was carried out for subsequent three 100 μm coating on the initial
surface. Totally, 500 μm of coating material was applied on the com-
bustion chamber components to convert the conventional engine into
low heat rejection engine. Similarly, other components were coated
with same procedure. Fig. 4 shows the thermally coated engine com-
bustion chamber components.
2.6. Role of post treatment system
From the available literature, it was noticed that the usage of bio-
diesel or biofuel in diesel engine leads to increase in engine exhaust
emission especially oxides of nitrogen due to presence of oxygen con-
tent in fuel. This was considered as one of the major drawback of using
alternative fuel in diesel engine. Therefore, selective catalytic reduction
(SCR) technique was said to be the promising solution to obtain reduced
NOx emission. In the engine tail pipe, aqueous urea was sprayed at
optimum flow rate to control emission. SCR setup consists of compo-
nents like solution storage tank, supply line, three way control valve,
small pump and sprayer. Urea (30%) was dissolved in distilled water
(70%) and stored in storage tank. During engine operation, aqueous
urea solution was sprayed continuously at optimum flow rate 3 ml per
minute. In addition, other exhaust emissions like hydrocarbon, carbon
monoxide and smoke were controlled by using catalytic converters.
Monolith converter was purchased from local distributer and modified
with initial SCR setup next to converter flange. This setup leads to
drastic reduction of engine exhaust emission without affecting the en-
gine performance parameters. Table 7 shows the details of post treat-
ment devices. Monolith converter was honeycomb in structure and
placed inside the stainless steel shell. It consists of three major sections
like hydrolysis, catalyst and clean up. Initially, SCR initiates by
spraying the aqueous urea on the exhaust gas from engine and enters
the hydrolysis section. Followed by, the exhaust gases were passed into
the catalytic converter where the catalytic reaction occurred. Further,
the gases moved to the clean-up area in the catalytic converter. Fig. 5
represents the schematic diagram of engine post treatment setup.
dissipation. Measurement of temperature from the experimental setup
was determined by installing K-type thermocouples at various junctions
and interlinked to digital indicator. All these sensors and devices used
were connected with National instruments make USB-6210 model
based data acquisition system for online data recording purpose and
storing. Engine emissions like CO, HC and NOx were measured using
AVL make 444 di-gas analyser. Smoke emission from engine was
measured using AVL make 437C free accelerator smoke meter. Engine
sound during operation was measured using HTC make SL1352 model
sound meter. Kistler make M111A22 model piezo electric pressure
sensors were used for the measurement of in-cylinder combustion
chamber pressure. Sensor was connected to charge amplifier and in-
terlinked with data logger for data conversion. Crank angle rotation of
engine was measured using Kistler make 2614C11 model encoder and
connected to data acquisition system.
Formerly, circulation of water to engine, calorimeter and dynam-
ometer were checked and fixed at optimum levels during engine op-
eration. Engine was ignited by battery ignition method and allowed to
run for about 30 min at part load to avail steady state operating con-
dition. Initially, diesel was used as a working fuel. During this opera-
tion, no leakage of water, lubrication oil and fuel were ensured for
safety precaution purpose. After attainment of steady state condition,
the readings were noted by increasing the load to the engine. Once the
observations with diesel was completed, the fuel was drained from tank
and fuel lines. Then, all components were cleaned with the help of air
compressor and reinstalled in the engine. Followed by, lemon oil was
refuelled in the tank and same procedure was used for data recording
purpose. To eradicate the presence of diesel, the engine was allowed to
run for more than 10 min at part load. Then, the lemon oil with cetane

3. Engine setup

Engine performance, combustion and emission characteristics were

analysed in a single cylinder, naturally aspired, four stroke, direct in-
jection, diesel engine. Table 8 provides the detailed specification of
experimental setup. Fig. 6 shows the schematic diagram of experi-
mental setup. Engine was coupled with Saj Test Plant make AG10
model eddy current dynamometer to produce brake power. The max-
imum torque and speed of eddy current dynamometer was 11.5 Nm and
10000 rpm respectively. During load application, water was circulated
under controlled water flow and pressure to avoid the heat production
from dynamometer. From water storage tank, the pump was used for
circulating water between junction and two rotometers with flow
controller. Based on manufacture recommendation, 750 LPH and 380
LPH water flow was fixed for engine rotometer and engine calorimeter
respectively. The load applied to the engine was measured using Sen-
sotronics make 60,001 model digital load cell indicator at a measure-
ment range of 0 to 230 kg. Engine fuel consumption was measured
using graduated burette connected to Broiltech make FCM and Differ-
ential pressure transmitter model fuel flowmeter was connected with
fuel reservoir at capacity of 3 L. Air consumption by engine was mea-
sured using Wika make SL1 model U-tube manometer interlinked with
air flowmeter from air box. Heat release rate from engine was measured
using calorimeter connected to another rotometer to control the heat Fig. 4. Thermally coated engine combustion chamber components.

7
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Table 7 Table 8
Details about post treatment devices. Experimental setup details.
Selective Catalytic Reduction Setup Equipment name: Engine
Name of the substrate Aqueous urea solution Make and model Kirloskar oil engines limited and TV1 model
Composition 30% of urea with 70% of water Type Single cylinder, four stroke, direct injection,
Flow rate 3 ml/minute (optimum) diesel engine
Bore × Stroke 87.5 × 110 (mm)
Catalytic Converter Setup
Rated output 5.2 kW
Dimension 110 mm × 85 mm
Speed 1500 rpm
Type Monolith honey comb
Compression ratio 17.5:1
Injection pressure 210 bar

Equipment name: Eddy Current Dynamometer

enhancer namely Pyrogallol was investigated by following the same
Make and model Saj Test Plant Pvt. Ltd. and AG10
procedure to observe the engine operation. Engine combustion chamber End flanges both side Cardon shaft model 1260 type A
components were disassembled and reinstalled with PSZ coated engine Torque 11.5 Nm
components. Followed by, the influence of cetane enhancer on coated Maximum speed 10000 rpm
engine was observed and recorded. Eventually, the engine exhaust was Maximum hot coil voltage 60
Cooling Water cooled
treated with post treatment system (SCR with catalytic converter) and
readings were measured. To provide reliable results, the engine test was Equipment name: Exhaust gas analyser
Make and model AVL 444 di- gas analyser
performed thrice with all test fuels and techniques and the end results
Measures CO, HC, NOx
were presented. Fig. 7 depicts the experimental methodology. Range CO: 0–10 (% volume), HC: 0–2000 (ppm),
During experimentation, the observed value may vary related to the NOx: 0–5000 (ppm)
true value under careful examination process too. This variation was Equipment name: Smokemeter
commonly referred as error and it may belong to either systematic or Make and model AVL 437C free accelerator smokemeter
random error category. The systematic error can be controlled by im- Measures Smoke density
plementing the correction factor or value. But, the random error was Range 0–100 (HSU)

calculated using statistical approach. This random error was calculated Equipment name: Soundmeter
by performing the test again and again with same operating conditions. Make and model HTC, SL- 1352 Professional Sound Level
Meter
The experimental uncertainty was calculated using root mean square
Accuracy, Frequency and dynamic ± 1.4 dB/31.5 Hz to 8 kHz/50 dB
method or propagation of uncertainty methods. Table 9 shows un- range
certainty analysis. The following Eq. (1) was used for measurement of Measuring level range Auto: 30 dB to 130 dB
uncertainty as follows, Sampling time 2 times/s

2 2 2
UR = ⎛ ∂R U1⎞ + ⎛ ∂R U2 ⎞ +⋯+⎛ ∂R Un ⎞
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ 4. Results and discussions
⎝ ∂Y1 ⎠ ⎝ ∂Y2 ⎠ ⎝ ∂Yn ⎠ (1)
In a single cylinder, direct injection diesel engine, low viscous
Where,
lemon oil (LO) was investigated to evaluate the performance, com-
bustion and emission characteristics. Then, the investigation was pro-
UR- total uncertainty of experimental result;
ceeded with lemon oil and cetane enhancer namely Pyrogallol (termed
R - Given function and depends on independent variables like Y1,
as LO + A). Further, the investigation of lemon oil was performed in
Y2…Yn
PSZ coated engine (termed as LO + C). Further, the investigation was
U1, U2…Un - independent variable uncertainties.
progressed with lemon oil and cetane enhancer in thermally coated
engine (termed as LO + A + C). To obtain reduced emission char-
Based on the analysis, total uncertainty was determined within the acteristics, the present work was continued with lemon oil and cetane
limit of ± 2.24%.
enhancer in thermally coated engine with post combustion treatment

Fig. 5. Schematic diagram of engine post treatment setup.

8
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Fig. 6. Schematic diagram of experimental setup.

Fig. 7. Experimental methodology.

system (termed as LO + A + C + PT). The observed results were
compared with neat diesel in unmodified diesel engine.
4.1. Performance characteristics:
The following section provides comprehensive discussions about
engine performance characteristics especially brake thermal efficiency
and brake specific fuel consumption for all samples and working con-
ditions considered for the present study.
4.1.1. Brake thermal efficiency
Fig. 8 shows the variation of brake thermal efficiency for all fuel
samples at engine part load and full load. In general, BTE deals with the
conversion of chemical energy in fuel into useful mechanical energy. In
engine, increased thermal efficiency leads to improved fuel economy
and high energy conversion efficiency. At part load, BTE for diesel, LO,
LO + A, LO + C and LO + A + C were observed as 16.7%, 18.9%,
19.25%, 19.31% and 20.4% respectively. Lemon oil showed better BTE
than diesel due to its promising physical and chemical properties. The
lower viscosity of lemon oil helps in complete combustion of fuel. A
slight improvement in BTE was noticed with lemon oil and pyrogallol
blend due to improved cetane number of fuel. Thermal barrier coating
leads to reduced heat loss from the combustion chamber which in-turn
leads to higher BTE with lemon oil than diesel. Lemon oil and

9
V. Karthickeyan, et al. Fuel 255 (2019) 115854

Table 9
Uncertainty analysis.
Parameters Measuring technique Accuracy Errors ( ± )

Load Strain gauge type load cell ± 10 N ± 0.2

Speed Magnetic pickup principle ± 10 rpm ± 0.1
Fuel flow measurement Volumetric measurement ± 0.1 cc ±1
Temperature Thermocouple ± 1 °C ± 0.15
Crank angle encoder Magnetic pickup principle ± 1 deg ± 0.2
Pressure Magnetic pickup principle ± 0.1 kg ± 0.1
Time Stop watch (Manual) ± 0.1 s ± 0.2
Soundmeter Frequency or pitch ± 1.4 dB ± 0.1
Manometer deflection Balancing of column of liquid ± 1 mm ±1
CO NDIR technique ± 0.02% volume ± 0.2
HC NDIR technique ± 10 ppm ± 0.1
NOx NDIR technique ± 12 ppm ± 0.2
Smoke Opacimeter ± 1 HSU ±1

biofuel namely pine oil in direct injection diesel engine [2]. Lower
viscosity of pine oil helps in better atomization of fuel than neat diesel.
Also, many research works affirmed that the thermal barrier coating
helps to attain improved thermal efficiency in DI diesel engine [22–24].

4.1.2. Brake specific fuel consumption

Fig. 9 shows the variation of brake specific fuel consumption for all
fuel samples at engine part load and full load. At part load, BSFC for
diesel, LO, LO + A, LO + C and LO + A + C were observed as
0.423 kg/kWh, 0.39 kg/kWh, 0.353 kg/kWh, 0.321 kg/kWh and
0.296 kg/kWh respectively. Due to better atomization, LO showed
lower BSFC than diesel. Decreased viscosity of lemon oil leads to better
spray formation inside the combustion chamber. A notable decrement
was noticed with lemon oil and pyrogallol blend due to improved ce-
tane number. In general, reduced BSFC was noticed with thermally
coated engine with biofuel due to enhanced in-cylinder temperature
which helps to attain high combustion chamber temperature. Lemon oil
and Pyrogallol in coated engine provoked the complete combustion of
Fig. 8. Variation of brake thermal efficiency against engine loads.
fuel which in-turn leads to lower fuel consumption than other operating
conditions. At full load, BSFC for diesel, LO, LO + A, LO + C and
LO + A + C were observed as 0.423 kg/kWh, 0.392 kg/kWh, 0.357 kg/
kWh, 0.321 kg/kWh and 0.295 kg/kWh respectively. All fuel samples
exhibited low BSFC due to conversion of energy into useful shaft work.
Lemon oil showed lower BSFC than diesel due to its promising fuel
properties. Lemon oil and Pyrogallol in coated engine exhibited lower
BSFC than other fuels. Similarly, reduced BSFC was noticed with an-
nona-eucalyptus oil blends in diesel engine due to its higher calorific
value and lower viscosity which leads to improved atomization of fuel
[25]. The effect of fuel additive namely di-tert butyl peroxide with palm
oil biodiesel exhibited lower fuel consumption due to reduced fuel
viscosity and density [26]. Engine operation with pumpkin seed oil
biodiesel in coated engine showed lower BSFC than conventional en-
gine due to high combustion chamber temperature which helps in
complete combustion of fuel [27].

4.2. Emission characteristics

Fig. 9. Variation of brake specific fuel consumption against engine loads.

Pyrogallol in PSZ coated engine showed higher BTE than former fuel
samples. The effect of cetane enhancer on LO with low heat rejection
technique helps to attain higher BTE than diesel. At full load, BTE for
diesel, LO, LO + A, LO + C and LO + A + C were observed as 26.9%,
29.3%, 29.9%, 30.15% and 31.07% respectively. Increased BTE was
observed with all test fuels and working conditions. Lemon oil and
Pyrogallol in PSZ coated engine exhibited higher BTE than diesel. Better
air-fuel mixing was observed due to low viscosity which helps in
complete combustion. Similar results were observed with low viscosity
Tail pipe engine emissions like carbon monoxide, unburnt hydro-
carbon, oxides of nitrogen and smoke were presented for detailed study
of engine emission characteristics with different fuel blends. The fol-
lowing section deals with the detailed discussion of emission char-
acteristics. AVL make 444 model gas analyser was used for the mea-
surement of HC, CO and NOx in terms of ppm, % volume and ppm
respectively. The measured raw data of emissions were converted into
g/kWh using the following Eq. (2) [28],
vi ∗ MWi ∗ CF ∗ 3600 ∗ ṁ ex
ṁ i =
MWex ∗ BP (2)
where,

10
V. Karthickeyan, et al.
Fig. 10. Variation of brake specific carbon monoxide against engine loads.
Fig. 11. Variation of brake specific hydrocarbon against engine loads.
Fig. 12. Variation of brake specific oxides of nitrogen against engine loads.
ṁ i - Specific mass emission of species in g/kWh,
vi - Volume of fraction of specific emission (in % volume or ppm),
MWi - Molecular weight of exhaust specific emission,
ṁ ex - Mass flow rate of exhaust gas from engine (sum of mass flow
rate of air and fuel mixture),
11
Fuel 255 (2019) 115854
MWex - Molecular weight of exhaust gas,
BP- Engine brake power in kW and
CF- Correction factor (related to relative humidity, pressure and
temperature in ambient air condition).
4.2.1. Brake specific carbon monoxide
Fig. 10 shows the variation of brake specific carbon monoxide for all
fuel samples at engine part load and full load. The major reasons for the
formation of BSCO emission were insufficient oxygen content and rich
air-fuel mixing. In addition, incomplete combustion of fuel in engine
leads to carbon monoxide emission. At part load, BSCO emission for
diesel, LO, LO + A, LO + C, LO + A + C and LO + A + C + PT were
observed as 5.95 g/kWh, 1.93 g/kWh, 1.79 g/kWh, 1.41 g/kWh, 1.10 g/
kWh and 0.76 g/kWh respectively. At full load, BSCO emission for
diesel, LO, LO + A, LO + C, LO + A + C and LO + A + C + PT were
observed as 4.19 g/kWh, 1.27 g/kWh, 1.15 g/kWh, 0.93 g/kWh, 0.71 g/
kWh and 0.54 g/kWh respectively. At all loads, diesel exhibited higher
BSCO than other fuel samples due to absence of oxygen in the fuel.
Lemon oil showed lower BSCO than diesel. This declined BSCO emis-
sion was due to improved air-fuel mixing, low viscosity and high ca-
lorific of LO and presence of oxygen in the prepared sample. Similar
trend of reduced CO emission was observed with low viscous biofuels
namely orange oil [29] and pine oil [2] in DI diesel engine. LO + A
blend experienced lower BSCO than diesel and LO. This reduced
emission was due to enhanced cetane number of fuel which in-turn
leads to complete combustion. Addition of cetane enhancer to LO lead
to declined fuel viscosity, enriched fuel spray formation and helps to
achieve effective conversion of carbon monoxide into carbon dioxide.
Lemon oil and pyrogallol in PSZ coated engine showed lower BSCO
emission than other fuel samples due to high combustion chamber
temperature in coated engine. On comparing with low load, all fuel
samples at full load experienced low BSCO emission due to complete
combustion fuel. The novelty of the present study includes the im-
plication of post treatment system with LO + A + C. With post treat-
ment, CC transforms the unburnt carbon monoxide in exhaust gas into
carbon dioxide. Many research works related to biofuels and biodiesels
operation in diesel engine showed low CO emission due to presence of
oxygen content in fuel [7,8,30–33]. Similarly, mustard oil biodiesel
with N-heptanol in DI diesel engine experienced low CO emission at all
loads due to improved combustion rate [34]. Neem oil in thermally
coated engine exhibited lower CO emission than uncoated engine due
to increasing combustion chamber temperature [35]. Usage of catalytic
converter with mahua biodiesel in diesel engine experienced low CO
emission [36].
4.2.2. Brake specific hydrocarbon
Fig. 11 shows the variation of brake specific hydrocarbon for all fuel
samples at engine part load and full load. In diesel engine, HC emission
was mainly due to incomplete combustion of fuel. The reasons for in-
complete combustion were insufficient oxygen in combustion region
and low combustion chamber temperature [37]. At part load, BSHC
emission for diesel, LO, LO + A, LO + C, LO + A + C and
LO + A + C + PT were observed as 0.197 g/kWh, 0.056 g/kWh,
0.042 g/kWh, 0.058 g/kWh, 0.037 g/kWh and 0.028 g/kWh respec-
tively. At full load, BSHC emission for diesel, LO, LO + A, LO + C,
LO + A + C and LO + A + C + PT were observed as 0.128 g/kWh,
0.037 g/kWh, 0.023 g/kWh, 0.031 g/kWh, 0.015 g/kWh and 0.012 g/
kWh respectively. At all loads, diesel experienced higher BSHC emission
than LO and other fuel samples. In general, biofuels operating in diesel
engine exhibited low BSHC emission due to presence of oxygen which
leads to enhanced combustion and longer ignition delay period. Ex-
istence of oxygen in LO leads to favouring factors of combustion like
high air-fuel mixing ratio, post combustion flame oxidation and high
flame speed [32]. LO and pyrogallol experienced lower BSHC emission
than LO. This reduction in BSHC emission was due to improved cetane
number of fuel which helps to attain enhanced combustion
V. Karthickeyan, et al.
Fig. 13. Variation of smoke against engine loads.
Fig. 14. Variation of in-cylinder pressure at engine full load condition.
characteristics. Followed by, LO in coated engine exhibited higher
BSHC emission than diesel and LO. At all loads, LO + A in PSZ coated
engine perceived lower BSHC emission than other fuel samples. This
reduction in emission was due to upgraded cetane number of fuel and
high combustion chamber temperature. With CC, LO + A in coated
engine showed lower BSHC emission due to improved combustion ef-
ficiency of fuel than diesel. Similar trend of declined HC emission was
noticed with blends of eucalyptus and biofuel at varying loads in diesel
engine [38,39]. Also, the results of LO + A were found similar with the
consequences of cashew nut shell liquid and pentanol blend [40]. Re-
duced HC emission was noticed with diesel and ethanol in yttria sta-
bilized zirconia coated engine [41]. Activated carbon based exhaust
treatment setup helps to achieve low HC emission with various alter-
native fuels in DI diesel engine [42].
4.2.3. Brake specific oxides of nitrogen
Fig. 12 shows the variation of brake specific oxides of nitrogen for
all fuel samples at engine part load and full load. The reasons for NOx
emission were existence of high oxygen molecules and superior flame
temperature [30]. In diesel engine, the production of NOx in the engine
exhaust was considered as the important aspect for the actual utiliza-
tion of biodiesel and biofuels [7]. At part load, BSNOx emission for
diesel, LO, LO + A, LO + C, LO + A + C and LO + A + C + PT were
observed as 8.37 g/kWh, 12.61 g/kWh, 11.35 g/kWh, 13.21 g/kWh,
10.73 g/kWh and 7.71 g/kWh respectively. At full load, BSNOx
12
Fuel 255 (2019) 115854
emission for diesel, LO, LO + A, LO + C, LO + A + C and
LO + A + C + PT were observed as 5.87 g/kWh, 9.81 g/kWh, 8.93 g/
kWh, 10.67 g/kWh, 8.11 g/kWh and 4.95 g/kWh respectively. At all
loads, diesel showed lower NOx emission than other fuel samples due to
scarcity of oxygen. LO experienced higher NOx emission than diesel.
This increased NOx was due to innate oxygen content and its low cetane
index property. Lemon oil with low cetane index leads to long ignition
delay period and thus creates more air-fuel accumulation during the
premixed combustion phase [6]. Therefore it leads to increase in the in-
cylinder pressure and combustion chamber temperature. Also, it was
noteworthy to mention that the oxides of nitrogen were directly pro-
portional to combustion chamber temperature. LO with Pyrogallol ex-
hibited lower NOx emission than LO because pyrogallol acts as a re-
ducing agent. LO with Pyrogallol in PSZ coated engine experienced
higher NOx emission than other fuel samples due to surplus oxygen
content in LO and high combustion chamber temperature incurred by
PSZ coated engine. With post treatment, LO and Pyrogallol with PSZ
coating showed lower NOx emission than diesel and LO. Separate se-
lective catalytic reduction (SCR) equipment was installed at the exhaust
tail pipe. As soon as the urea was introduced in the exhaust tail pipe,
urea was transformed into ammonia via two processes namely ther-
molysis and hydrolysis. The conversion mechanism of NOx based on
thermolysis and hydrolysis was portrayed in Fig. 5. Similar trend of
results were observed with winery waste biofuel (grape seed oil) in DI
diesel engine due to presence of high oxygen in fuel [43]. Also, Cym-
bopogon flexuosus biofuel with fuel borne additive showed lower NOx
emission than conventional engine [44]. Similar results were observed
by researchers while using SCR technique, highlighting it as one of the
promising technique for obtaining reduced NOx emission [14,36].
4.2.4. Smoke emission
Fig. 13 shows the variation of smoke emission for all fuel samples at
engine part load and full load. During combustion process, solid carbon
soot particles were evolved at fuel rich zone inside the combustion
chamber [45]. The major reasons for smoke emission were presence of
carbon atom present in the fuel and incomplete combustion of HC. At
part load, smoke emission for diesel, LO, LO + A, LO + C, LO + A + C
and LO + A + C + PT were observed as 52.8 HSU, 41.2 HSU, 38.4
HSU, 36.7 HSU, 33.2 HSU and 29.7 HSU respectively. At full load,
smoke emission for diesel, LO, LO + A, LO + C, LO + A + C and
LO + A + C + PT were observed as 79.8 HSU, 62.3 HSU, 56.9 HSU,
55.3 HSU, 49.5 HSU and 42.3 HSU respectively. At all loads, diesel
showed higher smoke emission than LO due to rich fuel mixture for-
mation. LO exhibited lower smoke emission at all loads due to presence
of oxygen content in fuel. This helps in proper atomization of fuel and
thus leads to complete combustion and increased oxidation process. LO
with pyrogallol showed lower smoke emission than diesel and LO due
to improved flow properties which helps to achieve better fuel atomi-
zation. LO in PSZ coated engine showed lower smoke emission than
other fuel samples due to improved combustion chamber wall tem-
perature and the in-built oxygen content in LO which helps to attain
complete combustion. At all loads, LO and pyrogallol in PSZ coated
engine experienced lower smoke emission than LO and diesel. This
reduction was due to influencing fuel properties and application of
thermal barrier coating technique. With post treatment, LO and pyr-
ogallol in PSZ coated engine showed lesser smoke emission than other
fuel samples. This reduction in smoke emission was due to presence of
oxidation catalyst in CC which enhanced oxidation of soot in the en-
gine. Many researchers concluded that the utilization of low viscosity
biofuel in diesel engine showed low smoke emission due to oxygen
content in fuel [2,3]. Annona methyl ester with fuel additive exhibited
lower smoke emission than diesel due to improved cold flow properties
of fuel [46]. Various fuel samples in thermally coated engine experi-
enced similar trend of reduced smoke emission due to high combustion
chamber temperature and presence of oxygen in fuel [24]. Blends of
pine oil with SCR and catalytic converter exhibited lower smoke
V. Karthickeyan, et al.
Fig. 15. Variation of heat release rate at engine full load condition.
emission due to amplified oxidation of soot [14].
4.3. Combustion characteristics
The combustion parameters like in-cylinder gas pressure and heat
release rate are used to explain about the engine combustion char-
acteristics of diesel engine with different fuels and discussed in the
following sections.
4.3.1. In-cylinder pressure
Fig. 14 shows the variation of in-cylinder pressure with crank angle
for all fuel samples at engine part load and full load. In diesel engine,
the proper mixing of air-fuel was determined by formation of in-cy-
linder pressure. The initial stage of combustion (premixed burning
phase) of fuel defines the in-cylinder pressure which was affected by the
evaporation of fuel during ignition delay period [47]. The evaporation
and combustion of fuel was highly influenced by its physical and
13
Fuel 255 (2019) 115854
chemical properties particularly viscosity. Low viscosity of fuel leads to
better air-fuel mixing and leads to improved combustion efficiency.
Diesel showed lower in-cylinder pressure than other fuel samples.
Lemon oil exhibited higher in-cylinder pressure than diesel due to
longer ignition delay period and presence of oxygen in the fuel. Low
cetane number of LO leads to longer ignition delay period. Similar trend
of results were observed with investigation of pine oil in DI diesel en-
gine owing to low cetane number which in-turn leads to longer ignition
delay period. LO with pyrogallol showed higher in-cylinder pressure
than LO and diesel. This increase in pressure was due to improved ce-
tane index of the fuel. The addition of PY to LO leads to longer ignition
delay period. LO in thermally coated engine showed higher cylinder
pressure than other fuel samples. PSZ coating transformed the con-
ventional engine into low heat rejection engine which in-turn leads to
enhanced combustion chamber temperature. LO and pyrogallol in PSZ
coated engine exhibited greater in-cylinder pressure than LO and diesel.
This increment in pressure was due to characteristic fuel properties
V. Karthickeyan, et al. Fuel 255 (2019) 115854

the follow of water. First law of thermodynamics was used to determine

HRR. Crank angle rotation was used to analyse HRR for all fuels and
100 cycle data was averaged to find the HRR for specific fuel. Eq. (4)
represents the heat release rate equation,

∂Q n γ ∂V 1 ∂P
= P + V
∂θ γ − 1 ∂θ γ − 1 ∂θ (4)

where,

P- in-cylinder pressure,
V- Cylinder volume in m3,
Θ-Crank angle rotation in degree,
Qn-Heat release rate and
γ (Cp/Cv)- Ratio of specific heat.

Fig. 16. Variation of sound level against engine loads.
with the addition of cetane enhancer and advanced combustion
chamber temperature with thermal barrier coating. In addition, fuel
droplet formation and fast evaporation of fuel samples leads to better
combustion characteristics. Longer ignition delay was noticed owing to
physical delay of fuel samples and rapid increase in cylinder pressure
after the start of combustion. This increased pressure was due to
thermal barrier coating which in-turn leads to complete combustion of
fuel. The admission of fine fuel droplet inside the combustion chamber
due to low viscosity of LO leads to longer ignition delay. Similarly, low
viscosity biofuel namely turpentine was investigated in diesel engine
showed higher in-cylinder pressure than diesel due to ignition delay
period and oxygen content in fuel [48]. Investigation of lemongrass oil
biofuel with ethanol exhibited higher in-cylinder pressure due to high
oxygen content inside combustion chamber which promotes complete
combustion of fuel [49]. In TBC engine, kapok oil exhibited higher in-
cylinder pressure than diesel due to high combustion chamber tem-
perature and oxygen content [50].
4.3.2. Heat release rate
Heat release rate (HRR) was measured using calorimeter setup
(shell and tube heat exchanger) attached in the engine exhaust tail pipe.
The setup contains one exhaust gas inlet and outlet with water inlet and
outlet for cooling purpose. Separate rotometer was connected to control
Fig. 15 shows the variation of heat release rate for all fuel samples at
engine part load and full load. In diesel engine, the rate of combustion
directly relates to extent of chemical energy released in the course of
combustion. The stages of combustion includes start of combustion,
ignition delay period and fuel burned in the premixed combustion zone.
The initial peak in the heat release rate curve depicts the premixed
combustion, the succeeding peak describes the diffusion combustion.
Diesel exhibited lower HRR than other fuel samples as ignition occurs
earlier due to high cetane index and calorific value of fuel. Initially,
negative values were noticed which represents the evaporation period
of fuel. LO exhibited higher HRR than diesel due to longer ignition
delay period. LO with pyrogallol experienced higher HRR due to im-
proved cetane number of fuel. LO in TBC engine exhibited higher HRR
than diesel due to high combustion chamber temperature and inherent
oxygen content in LO. In addition, low viscosity of LO helps in creating
fine fuel droplets and high temperature ambience leads to complete
combustion of fuel. Similar results were observed with neat orange oil
biofuel in direct injection CI engine due to longer ignition delay period
and inbuilt oxygen content in fuel [29]. Also, same orange oil with di-
ethyl ether exhibited higher HRR than other samples due to enhanced
cetane number which leads to increased ignition characteristics [9]. In
coated engine, waste cooking oil biodiesel showed higher HRR than
diesel due to high combustion chamber temperature [51].
4.3.3. Combustion noise
Fig. 16 shows the variation of sound level for all fuel samples at
engine part load and full load. In diesel engine, sound or noise was

Table 10
Comparison of present study findings with available literature.
Parameter Lemon oil Lemon peel oil [6] Orange peel oil [29] Lemongrass oil [5]

Major composition Trans-Isolimonene (C10H16) M-Mentha-4,8-Diene D-Limonene Citral terpenes

Chemical structure

Calorific value (MJ/kg) 42.76 41.51 34.65 37

Kinematic viscocity @ 40 °C 1.02 1.06 3.52 4.6
(cSt)
Engine used Kirloskar TV1 model direct Kirloskar TAF1 model direct injection Kirloskar make direct Kirloskar TV1 model direct injection
injection diesel engine diesel engine injection diesel engine diesel engine
BTE 31.07% 35.02% 31.07% 25.2%
CO 0.71 g/kWh 0.878 g/kWh 0.592 g/kWh 0.17% vol.
HC 0.012 g/kWh 0.0212 g/kWh 0.0243 g/kWh 58 ppm
NOx 4.95 g/kWh 7.95 g/kWh 16.738 g/kWh 715 ppm

14
V. Karthickeyan, et al.
classified as combustion noise, mechanical noise and noise from ac-
cessories. Combustion noise was produced during combustion of fuel by
creating an oscillation inside the combustion chamber by way of
modification in pressure values [52]. At full load, sound level for LO,
LO + A, LO + A + C, LO + C and diesel were recorded as 89.23, 91.67,
93.42, 94.85 and 98.09 dB(A) respectively. In general, any biodiesel
samples showed higher noise than diesel due to its inferior fuel prop-
erties. As LO was the low viscous oil, it exhibited lower noise level than
diesel at all loads. LO + A showed better noise level due to ignition
delay period occurrence. Addition of cetane enhancer with biofuel leads
to improved cetane number and fast evaporation of fuel after delay
period. TBC engine with lemon oil experienced higher noise level due to
ceramic layer inside combustion chamber which directly affects the
pressure level. LO with pyrogallol in PSZ coated engine showed lower
noise than other fuel samples. This reduction in noise level was due to
upgraded fuel properties and combustion temperature. Many works
revealed that the alternative fuel (especially biodiesels) application in
diesel engine experienced higher noise level than diesel due to inferior
physical and chemical properties [53–56].
5. Conclusion
In the present work, lemon oil was extracted using steam distillation
method and its physical and chemical properties were determined
based on ASTM biodiesel standards. Four stroke, single cylinder direct
injection diesel engine with eddy current dynamometer was used to
evaluate the performance, combustion, emission and noise character-
istics of LO. The following techniques namely addition of cetane en-
hancer, Thermal Barrier Coating, combined effect of cetane enhancer
and TBC and post treatment system (SCR and catalytic converter) were
discussed. Table 10 shows the comparison of the literature works with
the present observations. The following conclusions were drawn from
present research work as follows,
- At all loads, LO showed better performance characteristics than
diesel due to its promising physical and chemical properties. A slight
improvement in BTE and decrement in fuel consumption was no-
ticed with LO + A blend due to improved cetane number of fuel. LO
in thermally coated engine showed higher thermal efficiency and
lower fuel consumption than diesel due to enhanced in-cylinder
temperature. Lemon oil and pyrogallol in PSZ coated engine showed
higher BTE than former fuel samples.
- At all loads, LO showed lower BSCO than diesel owing to presence of
oxygen and low kinematic viscosity of the fuel. LO + A blend ex-
perienced lower BSCO than diesel. LO + A in PSZ coated engine
showed lower BSCO emission than other fuel samples due to high
combustion chamber temperature in coated engine. With post
treatment, CC transforms the unburnt carbon monoxide in exhaust
gas into carbon dioxide.
- LO + A experienced lower BSHC emission than LO due to improved
cetane number of fuel. LO + A in PSZ coated engine perceived lower
BSHC emission than other fuel samples due to upgraded cetane
number of fuel and high combustion chamber temperature. With
CC, LO + A in coated engine showed low BSHC emission due to
improved combustion efficiency of fuel.
- LO experienced higher NOx emission than diesel due to innate
oxygen content and its low cetane index property. LO + A exhibited
lower NOx emission than LO because pyrogallol acts as a reducing
agent. LO + A in PSZ coated engine experienced higher NOx emis-
sion than other fuel samples LO + A with PSZ coating showed lower
NOx emission than diesel and LO.
- LO exhibited lower smoke emission due to presence of oxygen
content in fuel. LO + A showed lower smoke emission than diesel
and LO. LO in PSZ coated engine showed lower smoke emission than
other fuel samples. LO + A in PSZ coated engine experienced lower
smoke emission than LO and diesel. With post treatment, LO + A in
15
Fuel 255 (2019) 115854
PSZ coated engine showed lesser smoke emission than other fuel
samples.
- LO exhibited higher in-cylinder pressure and HRR than diesel due to
longer ignition delay period and presence of oxygen in the fuel.
LO + A showed higher in-cylinder pressure and HRR than LO and
diesel due to improved cetane index of the fuel. LO in thermally
coated engine showed higher cylinder pressure and HRR than other
fuel samples. LO + A in PSZ coated engine exhibited greater in-cy-
linder pressure and HRR.
- Based on load conditions, sound was observed from the front posi-
tion of engine. Moreover, low viscosity of lemon oil leads to reduced
noise production in diesel engine.
From the present study, it was perceived that the LO biofuel may be
a promising alternative for conventional fuel in the prospect with ce-
tane enhancer, thermal barrier coating and post treatment techniques
to enhance the performance combustion and emission characteristics of
diesel engine. From the experimentation, it was observed that the
LO + A + C may be considered as the beneficial blend in-terms of its
performance and combustion characteristics. In addition,
LO + A + C + PT was considered as more advantageous than other
fuel samples on account of its emission characteristics.
Acknowledgment
The authors would like to express their thanks to University Grants
Commission- South Eastern Regional Office, Hyderabad, India for fi-
nancial support through Minor research project for teachers with grant
number 4-4/2013-14 (MRP- SEM/UGC- SERO).
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