Applied Thermal Engineering 58 (2013) 374e381

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Applied Thermal Engineering

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Desulfurization of diesel-like fuel produced from waste lubrication oil

and its utilization on engine performance and exhaust emission
Orhan Arpa a, Recep Yumrutaş b, *, Önder Kaşka c
a
Dicle University, Mechanical Engineering Department, Diyarbakir, Turkey
b
University of Gaziantep, Mechanical Engineering Department, 27310 Gaziantep, Turkey
c
University of Osmaniye Korkut Ata, Mechanical Engineering Department, Osmaniye, Turkey

h i g h l i g h t s

Diesel-like fuel (DLF) was produced from waste oil by pyrolitic distillation.

Oxidative desulfurization was applied to decrease sulfur level of the DLF.

Sulfur level of the DLF was decreased from 3500 ppm to 420 ppm.

The engine performance parameters of DLF were higher than those of low sulfured DLF.

Exhaust emissions (SO2, CO, NO) of low sulfured DLF lower than those of DLF.

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

Article history: In this study, desulfurization of diesel-like fuel (DLF) produced from waste lubrication oil, and the effects
Received 27 December 2012 of desulfurized fuel on engine performance and emissions were investigated experimentally. Firstly, the
Accepted 15 April 2013 DLF was produced by using a fuel production system and applying pyrolitic distillation method. After
Available online 6 May 2013
producing the DLF, oxidative desulfurization (ODS) method was applied at a temperature of 50  C in
order to decrease the amount of sulfur in the DLF. The sulfur level of the DLF was decreased from 3500 to
Keywords:
420 ppm after the application of ODS method. It was observed that temperature had an important effect
Engine performance
on decrement of sulfur content of the DLF. Secondly, characteristic tests such as density, kinematic
Exhaust emissions
Oxidative desulfurization
viscosity, heating value and flash point, sulfur content and distillation tests for the desulfurized fuel
Pyrolitic distillation named as low sulfur diesel-like fuel (LSDLF) are performed. Finally, the LSDLF and a commercial diesel
Recycling of waste oil fuel were used in a diesel test engine to examine their effects on engine performance and emission
parameters. In each test, performance and emission parameters for the fuels were measured using the
test engine and exhaust gas analyzer. The performance and emission test results indicated that torque,
mean effective pressure and brake thermal efficiency for the LSDLF were slightly higher while brake
specific fuel consumption, exhaust temperature and emissions of SO2, CO and NOx appeared to be lower
than those of the commercial diesel fuel. It was concluded that the LSDLF could be used in diesel engine
without any problems in terms of physico-chemical parameters, distillation and performance tests.
Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.

1. Introduction problems related to the petroleum fuels have appeared, some of

Energy demand increases due to industrialization and contin-
uously growing population in the world. Therefore, developing
countries are searching for new energy sources to meet their en-
ergy requirements. A great amount of energy is consumed by motor
vehicles. Currently, the main energy source of these vehicles is
petroleum-based fuels [1]. However in recent years, several
* Corresponding author. Tel.: þ90 342 3172520; fax: þ90 342 3601104.
E-mail addresses: yumrutas@gantep.edu.tr, yumrutas@gmail.com (R. Yumrutaş).
which are depletion of petroleum resources, increasing petroleum
prices, and environmental concerns, along with several other so-
cioeconomic issues. These problems have driven research to
develop alternative fuels from renewable resources that are
cheaper and environmentally acceptable [2]. Hence, many re-
searchers have tried to develop alternative fuel sources that
approximate the properties and performance of petroleum-based
fuels. The alternative fuel sources to petroleum should be techni-
cally feasible, economically competitive, environmentally accept-
able and easily available [3e5]. There are several types of waste fuel
sources such as waste oils, trees, plastics, tires, etc., which are

1359-4311/$ e see front matter Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.applthermaleng.2013.04.035
 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381
known as alternative fuel sources. However, they cannot be used as
engine fuel without purification and being converted into the fuel
to be used since they have many adverse effects on living beings
and environment [3e5]. The waste lubricant oils (WLOs) are one of
the important waste fuel sources. There will be several benefits
such as preserving petroleum resources, protecting the environ-
ment when the WLOs are used as engine fuel especially for gasoline
and diesel engines [6], reducing petroleum imports and thus
economizing on foreign exchange reducing greenhouse gas emis-
sions, and enhancing regional development and social structure
especially in developing countries [7]. The WLOs are potentially
inexhaustible energy sources since they are continuously used in
mechanical parts of machines. Waste lubricant engine oil is one of
the most important types of the WLOs since it will last as long as
there are engines in use whether it is originated from crude oil or
from other sources [8].
There is large amount of WLO discharged to the environment as
a result of their use. In the United States, around 7.6 million metric
tons per year in the world, 2.2 million in the European Union [9],
and about 500,000 tonnes of WLO in Turkey are used. The lubricant
oil demand in the world is about 40 million metric tons per year.
The waste generated oils represent more than 60% of used lubricant
oils. Therefore, waste oils are one of the most abundant pollutant
residues that are generated nowadays, reaching the value of 24
million metric tons per year [9]. Most of them are petroleum-based
oils, and the utilization rate is about 97% of the total lubricant oil
production [6]. The WLO contains a high amount of sulfur. The
primary product of combustion is sulfur dioxide (SO2), which is a
major environmental pollutant. The SO2 reacts with atmospheric
water vapor to produce sulfurous and sulfuric acids, both of which
contribute to acid rains. As a result of the widespread distribution
of the acid rain, the whole atmosphere may be threatened [3].
Therefore, it is necessary to decrease the amount of the sulfur
present in it. Sulfur removal from fuels has become a very impor-
tant and active research subject worldwide in the past decade since
the production and use of more environmentally friendly fuels have
been attracting increasing attentions in many countries [10]. The
regulations for sulfur contents in the liquid transportation fuels are
becoming more and more stringent [11]. This has been because of
the very stringent environmental regulations that have limited the
level of sulfur in diesel to less than 15 mg/kg since 2006 in the US,
less than 10 mg/kg since 2005 in Europe, and less than 50 mg/kg
since 2008 in Beijing and Shanghai in China [12]. Hydro-
desulfurization (HDS) processes are used to reduce the sulfur levels
in commercial fuels in today’s refineries [11]. However, the HDS
processes consume huge amount of energy because these pro-
cesses take place at high temperatures and high pressures, while
the oxidative desulfurization (ODS) technology is proposed due to
the less energy need. Because of its several advantages, ODS tech-
nology has drawn wide attention [13]. In this technology, there are
various types of oxidants in literature which include peroxy organic
acids, catalyzed hydro peroxides, inorganic oxidants such as inor-
ganic peroxy acids, peroxy salts, ozone, etc. [14]. It is necessary to
know that there are two critical problems related with the ODS
method. These problems are to reduce fuel quality because of un-
suitable oxidant and solvent selection causing increasing of un-
wanted side reactions and remove aromatic/olefinic compounds in
the fuel [15]. The other part of the study is about the effects of the
fuel produced from diesel-like fuel on engine performance and
emissions. There have been many studies performed to produce
alternative fuels from different fuel sources for gasoline and diesel
engines and to investigate the effects of the fuels on the engine
performance and emissions. Waste lubricating oils originated from
crude oil [16] and biodiesel from non-edible plant oils [17,18] were
used as a fuel sources for the diesel engine. Gasoline- and diesel-
375
like fuels have been produced from industrial and waste engine oils
[9,19], wood pyrolysis oils [20], waste fats and plant oils by using
pyrolysis process. Abdulvahitoglu and Aydin [21] prepared a fuel by
blending low sulfur diesel fuel with various types of substances
including rapeseed biodiesel, n-hexane and n-heptane. They
compared properties of the fuel blends with those of diesel fuel,
and performed engine performance and exhaust emission tests.
Arpa et al. [3,4] produced gasoline-like fuel (GLF) and diesel-like
fuel (DLF) by using WLO. These fuels were used in gasoline and
diesel engines to examine the effects of the fuels on performance
and emission of the both engines. However, the amount of sulfur in
the DLF was very high. In the study, sulfur amount in the DLF was
decreased by using hydrogen peroxide and formic acid. The
desulfurized fuel is named as low sulfur diesel-like fuel (LSDLF).
Physico-chemical parameters and distillation temperatures of the
LSDLF and a typical diesel fuel were measured, and they were
burned in a diesel test engine to compare the influences of the fuels
on performance and emissions.
2. Purified and pyrolitic distillation system
A purified and pyrolitic distillation system was used to purify
waste lubricant oil (WLO) from contaminants and to obtain DLF.
Schematic diagram of the system are shown in Fig. 1. The system
consists mainly of waste oil storage tank, pump and filters, reactor,
mixer, condenser and control unit. The waste oil storage tank was
used to collect WLO having several hazardous materials it. The WLO
was pumped from the tank to the reactor, and then it was made to
flow through the filters with 20 mm. Another part of the system, the
reactor, is the most important part of the system as thermal
treatment during heating of the WLO was performed there. The
reactor, designed for this type of studies and experiments, was a
fully insulated cylindrical chamber of inner diameter 30 cm and
height 40 cm. In order to be able to complete all characteristic and
performance tests, the reactor with the large volume for purpose of
producing 20 L of fuel was constructed. The reactor was isolated
with glass wool with a thickness of 5 cm to minimize heat loss.
Electrical heaters with a total heating capacity of 5 kW, which can
heat the waste oil sample up to 600  C, were placed around the
reactor container. The temperature or heating rate of the WLO in
the reactor can be controlled by the control unit adjusting voltage
to keep temperature of the oil at desired levels. Desired tempera-
tures were measured by means of thermocouple. Another part of
the system is a mixer that is used in the reactor. The mixer is
employed for blending the waste oil sample taken into the reactor
to obtain uniform temperature. Otherwise, there would be a tem-
perature layer within the reactor. Another important component of
the system is the condenser unit that is used to distillate the oil
vaporized in the reactor. A water-cooled condenser was used to
Fig. 1. Schematic diagram of the pyrolitic distillation system.
376 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381

condense the fuel vapor vaporized at temperature ranges between

140  C and 430  C.

3. Measurements and experimental setup

It is necessary to measure physico-chemical parameters of a

diesel fuel and produced LSDLF used in the experimental study,
performance and emission parameters to find the effects of the
fuels on engine performance and exhaust emission parameters. In
the experimental study, physico-chemical parameters of the fuels
such as; flash and fire points, viscosity, sulfur content, distillation
and heating value are measured. All measurements and experi-
mental setup are described in this section. The measurements are
explained under three sections as physico-chemical parameters of
fuel samples, performance and exhaust emission parameters.
3.1. Physico-chemical parameters of the fuels
Physico-chemical parameters of the produced LSDLF fuel sam-
ple such as density, viscosity, flash point, sulfur content, initial and
final boiling points (IBP and FBP), and lower heating value (LHV)
and its distillation test are very important in order to decide
whether the fuel can be used or not in an engine without any
problems. These tests were conducted in the Fuel Laboratory at
Mechanical Engineering Department of Gaziantep University, and
they are based on American Standards for Testing and Materials
(ASTM) methods. The IBP, FBP, distillation test [22], density [23] and
LHV [24] were determined in the fuel laboratory. Physico-chemical
parameters of the fuels measured are given in Table 1. In this study,
two types of fuels which are low sulfur diesel-like fuel (LSDLF) and
a commercial diesel fuel were used. Physico-chemical parameters
and distillation test results for the LSDLF and diesel fuel samples are
given in Table 1 and all the test results are discussed in Section 5.
3.2. Specifications of the test engine and its testing procedure
Engine performance and exhaust emissions tests of fuel samples
known as DLF and LSDLF were conducted on a Diesel test engine at
Vocational School of Higher Education in Batman, Batman Univer-
sity. Schematic drawing and picture of the test engine are shown in
Fig. 2. The diesel test engine and a hydraulic dynamometer con-
nected to the engine were used for this purpose. The test engine
was modeled as Rainbow-186 which is a single cylinder, four-
stroke, air cooled, and naturally aspired direct injection engine.
The cylinder has a bore of 86 mm and a stroke of 70 mm. The
maximum power output of the engine is 10 kW at 2000 rpm. The
Table 1
Physico-chemical parameters of DLF, LSDLF and diesel fuel.
Fig. 2. Schematic diagram of the test engine and exhaust analyzer. (1) Engine chassis,
(2) exhaust gas analyzing probe, (3) exhaust gas analyzer, (4) single cylinder diesel
engine, (5) load cell, (6) dynamometer, (7) tachometer, (8) control unit, (9) fuel burette,
(10) fuel container.
combustion system of the engine has a hole piston, direct injection,
and is medium-swirl type. The engine is equipped with a
mechanical-PF type fuel pump. The fuel injector has three holes
with an opening pressure of 196 bar. The engine is connected to
hydraulic dynamometer. The basic specifications of the engine are
shown in Table 2.
It is necessary to measure performance and emission parame-
ters to determine effect of the LSDLF fuel on engine performance
and emissions. For that reason, measuring equipments were cali-
brated. The test engine was run for 10 min to reach steady state test
conditions and the data recording started. The measurement was
performed when the engine started to operate faultless. The engine
was loaded partly and measurements were recorded at each
500 rpm speed interval.
3.3. Exhaust gas analyzer
Greenline 8000 modeled exhaust gas analyzer was used to
measure emissions exhausted from the test engine. The specifi-
cations of the analyzer are given in Table 3. The analyzer mea-
sures carbon monoxide (CO), sulfur dioxide (SO2), and nitrogen
dioxide (NOx) emissions with a sensitivity of 1 ppm, and also O2
and CO2 emissions with sensitivity of 0.1%. During the perfor-
mance tests, the engine was operated until it reached to opera-
tion temperature, the probe of the gas analyzer was placed in the
exhaust pipe. Then, the emission values measured by the analyzer
were printed out through a printer on the analyzer. The results
measured by the analyzer are given and discussed in the
following section.

Properties Test method Commercial DLF LSDLF

diesel fuel Table 2
Density at 15  C (kg/m3) EN ISO 12185 840 818 814 Main specifications of the test engine.
Kinematic viscosity EN ISO 3104 3.5 3.49 3.2
Engine model Rainbow-186
at 40  C (cSt)
Flash point ( C) EN ISO 2719 55 57 56 Engine type Four stroke
LHV (kJ/kg) ASTM D-4809 42,700 42,500 42,100 Fuel type Diesel
Sulfur amount (mg/kg) EN ISO 20884 650 3500 420 Bore 80 mm
Water (mg/kg) EN ISO 12937 120 130 115 Stroke 70 mm
Distillation ( C) EN ISO 3405 148e350 150e360 145e338 Swept volume 406 cm3
Recovered at 250  C, 65 20 28 Compression ratio 18:1
(% vol, max) Injection pressure 20 MPa
Recovered at 350  C, 85 90 95 Cooling type Air cooled
(% vol, min) Maximum torque 40 Nm at 2000 rpm
95% vol. recovered 360 360 350 Maximum power 10 kW at 2000 rpm
at ( C, max) Engine position Vertical
 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381 377

Table 3 with time. It is noticed from the figure that great amount of the
Technical features of Greenline 8000 exhaust gas analyzer. WLO treated at 330  C during one hour.
Parameter Sensor type Range Max. Accuracy
perception 4.2. Desulfurization tests
time (s)

O2 Electrochemical 0e25% 20 0.1% vol Sulfur amount in the DLF was very high according to sulfur test
CO Electrochemical 0e8000 ppm 50 <300 ¼ 10 ppm
result. It was necessary to decrease sulfur amount in any fuel under
NO Electrochemical 0e4000 ppm 40 <100 ppm ¼ 5 ppm
NOx Calculated 0e4000 ppm e e standard values. Therefore, desulfurization tests were primarily
SO2 Electrochemical 0e4000 ppm 40 <100 ppm ¼ 5 ppm carried out in the study. There are several effective approaches
CO2 Calculated 0e99.9% e e toward oxidative desulfurization of fuel oils, such as using H2O2/
CxHy NDIR 0e5% 20 5%
organic acids, H2O2/heteropolyacid, H2O2/Ti-containing zeolites,
Tgas Thermocouple K 0e1000  C e (0.3% rdg þ 0.3)
and other non-hydrogen peroxide systems [12]. Hydrogen peroxide
(H2O2) is widely used for oxidation of various organic compounds,
wherein a great deal of reactions proceeds with participation of
4. Results and discussions transition metal complexes as catalysts [25]. Much interest has
been shown over the last decade for the application of oxidative
In this study, the DLF was produced from WLO using pyrolitic desulfurization (ODS) to liquid fuels. The major organic acids used
distillation unit as shown in Fig. 1, and then an experimental study in the ODS are acetic acid and formic acid. The fuel is mixed with
for reducing the sulfur amount in the DLF was carried out using H2O2/acetic acid (peroxyacetic acid) and the oxidative reaction
hydrogen peroxide and formic acid. As a result of the study, LSDLF takes place below 100  C under atmospheric pressure [12]. For that
was obtained. Next, physico-chemical parameter, distillation, per- reason, an experimental study to decrease sulfur amount in the DLF
formance and exhaust emission tests were performed by using a was performed using hydrogen peroxide and formic acid with
diesel test engine and exhaust gas analyzer to examine the effects different rates in the ODS.
of the fuel on performance and emissions of diesel engine. A typical The mixture of 10 g of 98% hydrogen peroxide and 20 g of 30%
diesel fuel and LSDLF were used in the process to compare physico- formic acid was prepared, and 2, 4, 6, 8, and 10 g from the mixture
chemical parameters, performance and emission parameters. was added into the five samples of 100 ml DLF, respectively. The
Therefore, desulfurization of the DLF, physico-chemical parameters samples were heated up to 40, 50, 60 and 70  C under atmospheric
and distillation test results of the LSDLF and diesel fuel, perfor- pressure for 120 min. Then all samples were washed with 15 ml of
mance and emission parameters were tested. They are given in distilled water to remove unused oxidant in the fuel sample. Fuel
figures and tables and discussed separately in this section. samples staying at the upper layer of the container were used in
sulfur determination, and the results obtained are presented in
4.1. Pyrolysis procedure figures. Fig. 4 indicates variation of sulfur in the fuel samples with
respect to temperature and amount of formic acidehydrogen
It is known that pyrolysis conditions such as heating rate, time peroxide. It can be observed from the figure that sulfur reduces
and temperature of the WLO are very important. For example, from 3500 ppm to 2150 ppm when the ODS takes place with 10 g of
hydrocarbons constitutes the WLO do not decay into lighter hy- formic acidehydrogen peroxide at 50, 60, and 70  C. It can also be
drocarbons, and heavy hydrocarbon is obtained when heating rate seen that higher temperatures did not have any impact on the
is very high. Several pyrolysis processes were applied, and the most sulfur content in the DLF sample. It was determined that 10 g formic
suitable pyrolysis conditions were obtained. In this study, reactor acideH2O2 mixture at 50  C was a suitable condition to achieve
temperature first set up 330  C and WLO was kept in reactor for 1 h oxidation in the DLF sample. Sulfur amount at 50  C decreases to
at constant temperature of 330  C. Then, reactor temperature was the same level with 60  C and 70  C. This is desired condition for
increased 30  C in each 30 min, and final temperature was equal to heat demand. Since heat requirement at 50  C is lower than those of
420  C. The graph for relationship between temperature of the WLO the higher temperatures.
in the reactor and pyrolysis time is shown in Fig. 3. It is seen from In order to examine the effect of ODS time, an experiment was
the figure that temperature of the WLO increases approximately up carried out, and a mixture of 10 g formic acideH2O2 and DLF was
to 330  C while time reaches to 90 min. Its temperature stays kept at 50  C for a day. After one day, sulfur level of the sample was
constant at this temperature as the pyrolysis time reaches to measured as 1000 ppm. The test results indicate that time is very
150 min. After this time, temperature continues to increase again

4000
500
40 ºC
3500 50 ºC
400
60 ºC
Sulfur (ppm)
Temperature ( C)

3000 70 ºC
300
2500
200
2000
100 Reaction time: 120 min
1500
0 0 2 4 6 8 10
0 30 60 90 120 150 180 210 240
Hydrogen peroxide-formic acid (g)
Time, min
Fig. 4. Variation of sulfur level with hydrogen peroxideeformic acid for different
Fig. 3. Variation of WLO temperature with time during pyrolitic distillation process. temperatures.
378 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381

important on oxidation process. For this reason, hydrogen 400

peroxideeformic acid ratio was selected as 2/1, and sulfur-
350
removing process was repeated at 50  C for a day. Results obtained
from the test are shown in Fig. 5. It is observed that sulfur level 300

Temperature ( oC)
decreases rapidly with increasing amount of mixture of hydrogen
250
peroxideeformic acid at 50  C. Sulfur amount in the fuel decreased
from 3500 ppm to 420 ppm when the mixture of H2O2eformic acid 200
and the DLF sample was rested for 24 h. Diesel
150
DLF
100 LSDLF
4.3. Physico-chemical parameter tests
50
Physico-chemical parameters of fuels are very important for an 0 10 20 30 40 50 60 70 80 90 100
engine in order to decide whether the fuels will be able to use or Distilled volume (cm3)
not in the engine. Therefore, physico-chemical parameters of the
produced LSDLF, such as density, flash point, kinematic viscosity, Fig. 6. Distillation curves of DLF, LSDLF and a typical diesel fuel.

sulfur and water content, and LHV are tested, and results are given
in Table 1. They are reasonably closer to the values of standard
lower temperature. Since any fuel having lower density is lighter
diesel fuel. One of the most important physico-chemical parame-
than the other fuel. Distillation temperatures for the LSDLF for each
ters is LHV. The LHV of the LSDF is calculated as 42,100 kJ/kg ac-
volume or droplet are lower than those of the DLF. The curve for the
cording to ASTM D-4809 Standard. It is closer to LHV of diesel fuel
LSDLF follows a parallel curve for DLF with temperature difference
with a value of 42,700 kJ/kg in ASTM D-4809 Standard. It is also
between 5  C and 25  C. So, the distillation curve for the LSDLF
closer to the values given in literature for commercial diesel fuels as
approaches closer to the curve for the diesel fuel. It can be
42,210 kJ/kg [26], 43,000 kJ/kg [27,28], 43,060 kJ/kg [29], and
concluded that the LSDLF can be used efficiently in diesel engines,
43,500 kJ/kg [30]. Distilled volumes or temperatures corresponding
and there will be no problems in the performance of the engine.
to values given in these Standards are also presented in Table 1. It is
Thermal and physical properties of the sample given in Table 1
considered that a diesel fuel having these properties and LHV will
support these claims. Distillation temperature increases versus
not cause any problems in engine combustion equipment or
distilled volume smoothly and gradually. This gradual increment is
decrease in performance of the engine. This idea can be explained
important because starting ability and warm-up property of the
using distillation results of the LSDLF.
fuel is evaluated by the evaporation temperatures of 20e70%
vaporization region of the distillation curves [29]. Each droplet of a
4.4. Distillation tests fuel should be distilled in a regular and increasing temperature. A
fuel sample which is distilled in a constant temperature or very
Distillation is the process of heating a liquid until it boils, narrow temperature band is not desired fuel [29,31], since it will
capturing and cooling the resultant hot vapors, and collecting the result in an immediate burning and a high rate of pressure rise.
condensed vapor. It can also be defined as a method of separating of
mixtures based on differences in volatilities of components in a
4.5. Performance tests
boiling liquid mixture. It is a powerful tool, both for the identifi-
cation and the purification of organic compounds by separating
The effects of the produced LSDLF on engine performance and
them from non-volatile or less-volatile materials. Therefore,
exhaust emissions were investigated in the experimental study.
distillation test results give more important ideas about combus-
Therefore, a four-stroke, direct injection, naturally aspirated single
tion and engine performances, since this curve is an indication of
cylinder diesel engine was used. Schematic drawing and the main
how ignition in an engine will take place. It can be decided whether
specifications of the engine are given in Fig. 2 and Table 2,
the fuel can be used in engines or not by looking at the curve. The
respectively. Two fuel samples, the LSDLF and commercial diesel
distillation curves of DLF and LSDLF obtained by decomposing from
fuel to evaluate performance and emission parameters, were used
the waste oil sample and a typical diesel fuel are shown in Fig. 6. It
in the test engine. Performance parameters such as torque, brake
can be seen from the figure that the curve of the LSDLF resembles,
mean effective pressure (BMEP), brake specific fuel consumption
and is almost parallel to that of the diesel fuel. It can be observed
(BSFC), and thermal efficiency were obtained using expressions
from the figure that the LSDLF having lower density distillates at
given in Refs. [3e5]. The data for the LSDLF and diesel fuel are given
in separate figures for comparison.
Figs. 7e10 indicate variations of torque, BMEP, brake thermal
4000 efficiency and BSFC with engine speed, respectively. It is observed
from Figs. 7e9 that the torque, BMEP, and thermal efficiency for the
Reaction time: 24 h LSDLF are slightly higher than those of diesel. On the other hand,
3000
Fig. 10 shows that BSFC is lower than that of diesel. There is no
Sulfur (ppm)

significant difference in performance parameters when the LSDLF

2000 and diesel fuel are used in the engine. Heating capacities supports
the low difference in performance parameters, because, there is a
1000 reasonably low difference in LHV’s for the LSDLF and diesel fuel.
This shows that there is no significant power reduction in the en-
gine when the LSDLF is used in the engine, but sulfur amount in
0
0 2 4 6 8 10 emissions for the LSDLF will be higher than that of the diesel fuel.
Mixture of hydrogen peroxide and formic acid (g) As it is seen from Figs. 8 and 9, thermal efficiency and BMEP in-
crease with the engine speed and reach to the maximum value at
Fig. 5. Variation of sulfur level with hydrogen peroxideeformic acid at 50  C. 2500 rpm, whereas the BSFC shown in Fig. 10 reaches the minimum
 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381 379

33 50

45

Brake thermal efficiency (%)

40
Torque (Nm)

32 35

30
Diesel
Diesel
25
LSDLF
LSDLF
31 20
1500 2000 2500 3000 1500 2000 2500 3000
Engine speed (rpm) Engine speed (rpm)

Fig. 7. Effects of LSDLF on the engine torque. Fig. 9. Variation of brake thermal efficiency with engine speed.

and emission amount were measured continuously during the test.

value at the same speed. However, the maximum torque values for
Since they effect performance of the engine used in the test, and
LSDLF and commercial diesel fuel obtained in speed of 2000 rpm
give an idea about it. The exhaust gas temperature (EGT) and
are 32.46 and 32.37 Nm, respectively.
emissions such as carbon monoxide (CO), carbon dioxide (CO2) and
Fig. 10 shows the variations in the BSFC of both diesel fuel and
sulfur dioxide (SO2), nitrogen oxide (NOx) were measured in the
LSDLF with respect to the engine speed. The BSFC is the ratio of the
experimental study.
fuel consumption to the brake power of the engine, which is an
indicator showing the amount of fuel supplied to the engine per
4.6.1. Exhaust gas temperature
unit power production. Due to the fact that the Tb, BMEP and hbt are
The exhaust gas temperature indicates the effective use of the
directly proportional, but BSFC is indirectly proportional with the
heat energy of a fuel used in engine cylinders. The variations of
engine brake power. The BSFC for the LSDLF operation is on an
exhaust gas temperature with engine speed for LSDLF and diesel
average 3.7% lower than that for the diesel fuel. It is considered that
fuel are shown in Fig. 11. It is observed that as the engine speed
this decrease in BSFC originates from the higher mean distillation
increases exhaust gas temperature also increases for both fuels.
temperature for the LSDLF. Since the higher distillation tempera-
When the LSDLF sample is used in the engine, the exhaust tem-
ture increases combustion efficiency, which increases torque, brake
perature is lower than that of the diesel fuel sample, and it in-
power, thermal efficiency and BMEP, and decreases the BSFC, which
creases with the engine speed. The measured exhaust temperature
is discussed in Refs. [4,31]. As a result, there are small differences in
varied between 368  C and 450  C for the LSDLF compared to 397  C
torque, BMEP, thermal efficiency and BSFC values for the LSDLF and
and 477  C for diesel indicating remarkable variation in exhaust
diesel fuel. Torque, BMEP and thermal efficiency for LSDLF are
temperature. An increase in the exhaust temperature or heat loss in
higher than those of diesel fuel while the BSFC is lower than that of
the exhaust pipe reduces the conversion of heat energy of the fuel
diesel fuel. This is an important criterion that makes the LSDLF
to work [2]. The low value of engine exhaust gas temperature in-
advantageous in terms of performance parameters. Test results
dicates that, compared to diesel fuel, the LSDLF burned better in the
clearly indicate that the LSDLF has a positive effect on the perfor-
cylinders. Since, atomization of the LSDLF will be better than that of
mance parameters of the engine, and it can be safely used as a fuel
the diesel fuel due to density, which results better combustion
in diesel engines without any problems.
performance. Higher engine performance may yield lower exhaust
temperature. Another possible explanation for the reduction in
4.6. Exhaust gas temperature and emission tests exhaust gas temperature is due to the LHV of LSDLF as compared to
the standard diesel fuel. Since LHV of the LSDLF is slightly lower
Exhaust temperature and emission parameters, and their than that of the diesel fuel. Consequently, these factors are
amounts in the exhaust are extremely important in addition to considered to reduce the exhaust gas temperature.
engine performance. For that reason, engine exhaust temperature

350
1050
300
BSFC (g/kWh)

1000 250
BMEP (kPa )

200
950 Diesel
150 Diesel
LSDLF LSDLF
100
900
1500 2000 2500 3000
1500 2000 2500 3000
Engine speed (rpm) Engine speed (rpm)
Fig. 8. Effects of LSDLF on the brake mean effective pressure. Fig. 10. Variation of BSFC versus engine speed for the LSDLF and diesel fuel.
380
550
Exhaust temperature ( oC)
500
450
400
Diesel
350
LSDLF
300
1500 2000
Engine speed (rpm)
Fig. 11. Variation of exhaust temperature with engine speed.
4.6.2. Exhaust emission tests
When a fuel is burned in engine cylinders, some main com-
pounds or substances can be exhausted from the engine. These
substances are known as CO2, O2, H2O, N2, CO, SO2, NOx, unburned
hydrocarbon (HC) and emissions and particulates. As a result of the
combustion, some of them are expected to come out such as CO2,
H2O, O2 and N2, and some of them are not desired substances such
as CO, NOx, SO2, and HC. Since, they have negative effects on the
environment and combustion efficiency. In this study, variations of
the SO2, CO and NOx values in the exhaust emissions for LSDLF and
diesel fuel samples are measured by exhaust analysis device, and
variation of them are presented with engine speed in Figs. 12e14,
respectively.
SO2 values are of great importance in terms of energy and the
environment. Therefore, it is necessary to decrease the sulfur
amount of fuels to standard values. As a result of the oxidative
desulfurization study, sulfur amount of DLF is decreased to a value
of 420 ppm, and it is named as LSDLF. After it was burned in test
engine, SO2 values in the engine emissions were measured, and it is
depicted in Fig. 12. It is seen from the figure that the SO2 values for
the LSDLF are lower compared to those of diesel fuel. The result is
normally expected results, because the amount of sulfur in LSDLF is
lower than that of the diesel fuel, which is supported by Table 1.
This is positive effect on environment, because the lower SO2 gases
release to the atmosphere decrease sulfuric acid (H2SO4) formation
by reacting with water vapor in the atmosphere, and they harm all
living things.
The effects of LSDLF on CO and NOx emissions with engine speed
are shown in Figs. 13 and 14. The CO emission from the engine
operated with the LSDLF is lower than those of diesel for all engine
speeds. However, the NOx is lower for the engine speed that is
higher than 2500 rpm. While minimum values of the CO are
3500
Diesel
3000
LSDLF
2500
SO2 (ppm)
2000
1500
1000
500
1500 2000
Engine speed (rpm)
Fig. 12. Effects of LSDLF on SO2 emission.
O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381
2
Diesel LSDLF
CO (%)
1
0
2500 3000 1500 2000 2500 3000
Engine speed (rpm)
Fig. 13. Effects of LSDLF on CO emission.
300
Diesel
200
NOx (ppm)
LSDLF
100
0
1500 2000 2500 3000
Engine speed (rpm)
Fig. 14. Effects of LSDLF on NOx emission.
measured as 0.3 and 0.61 ppm, minimum values of NOx are
measured as 68, and 74 ppm at 2000 rpm for the LSDLF and diesel
fuel, respectively. As the engine speed exceeds the 2000 rpm, both
the CO and NOx increase. The formation of the NOx highly depends
on combustion temperatures, the oxygen concentration and resi-
dence time for the reaction to take place [29,31,32]. It is considered
that nitrogen (N2) and oxygen (O2) in the combustion chamber
dissociate into their atomic states, and participate in a series of
reactions at high combustion temperature [31]. This situation is
supported by Fig. 11. It is seen from Fig. 11 that the exhaust tem-
perature for the LSDLF is lesser than that of diesel fuel sample for all
engine speeds. CO emission in the exhaust depends on several
parameters such as chemical structure and homogeneity of the fuel,
insufficient time of burning, low and high temperatures and
insufficient air and dissociation due to high combustion tempera-
ture. Insufficiency of air is the most important parameter, for it
leads to the rejection of the CO from the exhaust without being
converted into CO2 [3,33]. It is considered that deficiency of oxygen
in combustion chamber causes emissions of the CO, since the CO
decreases to minimum value when the O2 amount reaches to the
maximum value. It is clear that if air fuel ratio or O2 in the com-
bustion chamber is increased, CO amount will also decrease.
5. Conclusions
An experimental investigation was performed to decrease sulfur
2500 3000 amount in the diesel-like fuel (DLF), and to evaluate the perfor-
mance and exhaust emission levels of desulfurized fuel named as
low sulfured diesel-like fuel (LSDLF). The DLF was produced from
the waste lubrication oil by using pyrolitic distillation method.
 O. Arpa et al. / Applied Thermal Engineering 58 (2013) 374e381
After oxidative desulfurization (ODS) process was applied to the
DLF, characteristic, performance and emission tests for the LSDLF
and a commercial diesel fuel were carried out by using testing
equipments and a diesel test engine. The most important results are
concluded as follows:
1. It was observed that cracking temperature and time were very
important effects on cracking of the waste lubrication oil (WLO)
thermally into lighter compounds, and great amount of the
WLO was cracked substantially at a temperature of 330  C and
during one hour period.
2. The sulfur level of the DLF was decreased from 3500 to
420 ppm after applying the ODS process at a temperature of
50  C. It was concluded that temperature and amount of
hydrogen peroxideeformic acid had an important effects on
decrement of sulfur content of the DLF. It was obtained that the
sulfur level of the LSDLF was lower than that of the DLF and
diesel fuel used in the test.
3. When the LSDLF was used in the test engine, torque, brake
mean effective pressure and brake thermal efficiency were
slightly higher than those of diesel fuel while the brake specific
fuel consumption was lower. It was determined that torque and
brake mean effective pressure reached to the maximum value
while brake specific fuel consumption was at minimum in
2000 rpm.
4. Although the engine performance parameters for both fuel
samples were approximately closer to each other, the exhaust
emission values for the LSDLF such as CO, NOx and SO2 were
lesser. Therefore, it was concluded that the LSDLF was lesser
pollutant than diesel fuel used in this study.
5. It is concluded that studies on how to reduce SO2, CO and NOx
compounds which are exhausted as a result of ignition of any
fuel in a combustion chamber will be an important gain for
environmental values and energy consumption, and this will
also contribute to world’s economy positively.
Acknowledgements
This study is performed in the scope of 105M284 numbered
research project supported by The Scientific and Technological
_
Research Council of Turkey (TÜBITAK). The authors would like to thank
_
TÜBITAK for financial support and great contribution to our work.
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