PHD1

Fuel 156 (2015) 119
Contents lists available at ScienceDirect
Fuel
journal homepage: www.elsevier.com/locate/fuel
Impact of properties of vegetable oil, bio-diesel, ethanol and n-butanol

on the combustion and emissions of turbocharged HDDI diesel engine
operating under steady and transient conditions
Dimitrios C. Rakopoulos, Constantine D. Rakopoulos , Evangelos G. Giakoumis
Internal Combustion Engines Laboratory, Department of Thermal Engineering, School of Mechanical Engineering, National Technical University of Athens (NTUA), Zografou Campus,
9 Heroon Polytechniou Street, 15780 Athens, Greece
h i g h l i g h t s
Combustion and emissions in heavy-duty diesel at steady and transient operation.
Fueling with vegetable oil, bio-diesel, ethanol and n-butanol diesel fuel blends.
Decrease of smoke with all bio-fuels blends at steady and transient conditions.
Increase of NOx with vegetable oil and bio-diesel, and decrease with ethanol and n-butanol at steady conditions.
Increase of NOx with all bio-fuels at transient conditions.
a r t i c l e
i n f o
Article history:
Received 20 November 2014
Received in revised form 11 April 2015
Accepted 14 April 2015
Available online 22 April 2015
Keywords:
Turbocharged HDDI diesel
Combustion and emissions
Vegetable oil and bio-diesel
Ethanol and n-butanol
Steady and transient operation
a b s t r a c t
The present work evaluates the impact of properties of four very common bio-fuels, viz. vegetable oil
(cottonseed), or its derived (methyl ester) bio-diesel, or ethanol, or n-butanol, in blends of various proportions with diesel fuel, on the combustion and exhaust emissions of a fully instrumented, six-cylinder,
four-stroke, heavy-duty direct injection (HDDI), Mercedes-Benz bus diesel engine, bearing a waste-gate
turbocharger with after-cooler, running under steady and transient conditions. Under steady-state operation, exhaust smoke, nitrogen oxides (NOx), carbon monoxide (CO), and total unburned hydrocarbons
(HC) were measured and compared with those of the baseline operation (with neat diesel fuel) and
among themselves. Fuel injection, combustion chamber pressure, and heat release rate (HRR) diagrams
revealed interesting features of the combustion mechanisms. These results and the different physical
and chemical properties of those bio-fuels are used to aid the interpretation of the observed engine
behavior. As regards the transient engine operation, measurements for three accelerations tests were
examined with the engine fueled on bio-diesel or n-butanol diesel fuel blends. The test bed was complemented with fast response instruments to capture the development of key engine and turbocharger variables, depicted in analytical diagrams, using ultra-fast response instrumentation for the instantaneous
measurements of the exhaust NO and smoke opacity. Again, these results and the different physical
and chemical properties of bio-fuels are used to aid the interpretation of the engine behavior. Finally,
a comparison is made for the inuence of bio-fuels properties (bio-diesel and n-butanol) on the NOx
and smoke emissions between steady-state and transient operating conditions, under the recognition
of the different non-fuel factors affecting the transient operating schedules.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Stringent imposed emissions regulations legislated in various
countries have forced researchers or engineers working in the
automotive or energy industry, to focus their interest either on
Corresponding author. Tel.: +30 210 7723529; fax: +30 210 7723531.
E-mail address: cdrakops@central.ntua.gr (C.D. Rakopoulos).
http://dx.doi.org/10.1016/j.fuel.2015.04.021
0016-2361/ 2015 Elsevier Ltd. All rights reserved.
the domain of engine- [1] or fuel-related techniques [2]. The latter

include alternative gaseous fuels of renewable nature [3] or oxygenated fuels that can mitigate emissions, used either in diesel or
spark-ignition engines [4,5], or in homogeneous charged compression ignition (HCCI) [6] combustion systems.
Todays diesel engines are well established as the dominating
power-train solution in the world market. This is attributed to
the substantial improvements of these engines in terms of specic
D.C. Rakopoulos et al. / Fuel 156 (2015) 119
Nomenclature
A/C
b.m.e.p.
BC
BUT
CA
CLD
CO
DI
ETH
FSO
aftercooler
brake mean effective pressure
cottonseed bio-diesel
n-butanol
crank angle
chemiluminescent detector
carbon monoxide
direct injection
ethanol
full scale output
fuel consumption and reduction of pollutant emissions. This has

been achieved, over the last years, by following various engineor fuel-related techniques [2]. Especially for the reduction of pollutant emissions, attention is paid to alternative fuels with main
emphasis on bio-fuels [2].
The turbocharged diesel engine is currently the preferred
power-train system in medium and medium-large unit applications (trucks, land traction, ship propulsion, electricity generation,
etc). Moreover, it is continuously increasing its share of the highly
competitive automotive market, having already ensured a share
comparable to that of the gasoline engine in Europe [1]. The most
attractive feature of the diesel engine is its overall very good fuel
efciency, which can surpass a value of 40% in vehicular applications and 50% in large, two-stroke units used for marine propulsion
or electricity generation. Thus, diesel engines achieve much lower
fuel consumption and reduced carbon dioxide emissions than their
similarly rated spark-ignition counterparts.
Traditionally, the study of diesel engine operation has focused
on steady-state performance, with less attention paid to transient
operation. However, the majority of daily driving schedules
involves transient conditions with only a very small portion of a
vehicles operating pattern being truly steady-state, e.g. when
cruising on a motorway. Thus, the experimental and modeling
investigation of diesel engine transient operation has turned out
to be an important objective for engine manufacturers, intensied
by the signicant deviations experienced when comparing instantaneous transient emissions with their quasi-steady counterparts
[1,79]. Ref. [10] reviewed thermodynamic diesel engine simulations including emissions during transient operation and their
comparison with steady-state conditions.
Although experimental studies of transient cycles are of particular importance [1], they provide mean values of each emitted
pollutant and so conceal the inuence of each individual speed
or load change in the cycle. Therefore, the importance of understanding and reducing transient emissions separately for each
acceleration or load acceptance in the cycle becomes obvious.
The fundamental aspect of transient conditions lies in their operating discrepancies compared with the respective steady-state ones,
i.e. operation at the same engine speed and fuel pump rack position. Whereas during steady-state operation, engine speed and
fueling and, hence, all the other engine and turbocharger properties remain essentially unaltered, on the contrary under transient
conditions both the engine speed and fuel supply change continuously. Consequently, the available exhaust gas energy varies,
affecting turbine enthalpy drop and, through the turbocharger
shaft torque balance, the boost pressure and air-supply to the
engine cylinders is inuenced. However, due to various dynamic,
thermal and uid delays in the system (mainly originating in the
turbocharger moment of inertia - turbocharger lag), combustion
air-supply is delayed compared to fueling, thus affecting adversely
torque build-up and emissions [1].
HC
HDDI
HRR
HSDI
LHV
NO
NOx
TDC
T/C
VC
total unburned hydrocarbons

heavy-duty direct injection
heat release rate
high-speed direct injection
lower heating value
nitric oxide
nitrogen oxides
Top Dead Center
turbocharger
cottonseed (vegetable) oil
However, the vital issue of emissions overshoot during transients [7] has not been investigated adequately, owing to the need
for highly complicated, sophisticated and costly experimental
equipment, such as fully-automated test beds with electronically
controlled dynamometers and fast response exhaust gas analyzers.
As a result, a relatively small amount of experimental work has
been reported [11,12].
Besides, dwindling crude oil reserves and their increasing prices
have placed sensitive loads on the trade balances of non-oil producing countries, presenting a threat to the existence of the developing and industrialized countries. Thus, the development of
alternative fuel sources has drawn the vivid attention in various
countries, with particular emphasis on the bio-fuels that possess
the added advantage of being renewable fuels that can be replenished through the growth of plants or production of livestock,
showing an ad hoc advantage in reducing the emitted carbon dioxide [3]. Bio-fuels made from agricultural products (oxygenated by
nature) may not only offer benets in terms of exhaust emissions,
but also reduce the worlds dependence on oil imports, with local
agricultural industries supported and farming incomes enhanced.
Among those, liquid bio-fuels as for example vegetable oils or
their derived bio-diesels [1318], ethanol [1921], butanol [22
24], and diethyl ether [25,26] are considered as very promising
bio-fuels for engines, as reported in these works dealing with
steady-state diesel engine operation. Experimental studies of emission measurements during transient operation when using biodiesel blends appear in [2731] and with n-butanol blends in
[32], which nonetheless focus on transient cycle operation and
hence provide mean values of each emitted pollutant, concealing
the impact of each individual speed or load change in the cycle.
Results for smoke opacity during various individual transients (as
the ones considered here) using either vegetable oil methyl ester
or ethanol diesel fuel blends are reported in [33,34].
The advantages of vegetable oils as diesel fuel are the minimal
sulfur and aromatic content, and the higher ash point and lubricity. Their disadvantages include primarily the very high viscosity,
the higher pour point, and the lower cetane number, caloric value
and volatility [35,36]. Their major problem is the highly increased
viscosity, 1020 times greater than normal diesel fuel, for which
the following methods are adopted to cope with: mixing in small
proportions with diesel fuel, micro-emulsication with methanol
or ethanol, preheating, cracking, and conversion into bio-diesels
mainly via the transesterication process [37]. The advantages of
bio-diesels as diesel fuel are the minimal sulfur and aromatic content, and the higher ash point, lubricity and cetane number,
whereas their disadvantages include the higher viscosity (though
much lower than the vegetable oils one), the higher pour point,
the lower caloric value and volatility, the hygroscopic tendency,
and the lower oxidation stability [38,39]. This group has reported
works on the performance and emissions of the present turbocharged, HDDI diesel engine, under steady-state conditions,
when fueled with blends of diesel fuel with vegetable oils [40] or
bio-diesels [41].
Because of its high octane number, ethanol (CH3CH2OH) is a
good spark-ignition engine fuel, but it is true that it has been considered (rather vividly) and experimented also as supplement fuel
in diesel engines, as reported in review paper [42]. It is a bio-mass
based renewable fuel, which can be produced by alcoholic fermentation of sugar from various vegetable materials or agricultural
residues. While anhydrous ethanol is soluble in gasoline, additives
must be used to ensure solubility of ethanol (that is highly hydroscopic) in diesel fuel under a wide range of conditions [43].
Compared to diesel fuel, it possesses lower ash point, caloric
value and viscosity (and lubricity), while its cetane number is very
low [44]. This group has reported work on the performance and
emissions of the present diesel engine, under steady-state conditions, when fueled with blends of diesel fuel with ethanol [45].
Like ethanol, butanol is a biomass based renewable fuel that can
be produced by alcoholic fermentation of the biomass feedstock
used for ethanol production. Butanol possesses less hydrophilic
tendency, higher heating value, higher cetane number, lower vapor
pressure, higher viscosity (and lubricity) and (almost perfect) miscibility than ethanol [46]. Thus, butanol has properties much closer
to diesel fuel than ethanol, rendering it preferable for blending
with conventional diesel fuel. Unlike vegetable oils, bio-diesels or
ethanol, it has been experimented much less on diesel engines.
However, the relevant literature on the subject is increasing at
amazing rates in the last years [47]. The isomer that has most been
experimented with and used in the present study is 1-butanol, also
better known as n-butanol (normal butanol), having a straight
chain structure with the hydroxyl group at the terminal carbon
(CH3CH2CH2CH2OH) [48]. This group has reported work on the
performance and emissions of the present diesel engine, under
steady-state conditions, when fueled with blends of diesel fuel
with n-butanol [49].
Furthermore, this group has reported works concerning the
emissions of the present diesel engine when fueled with blends
of diesel fuel with bio-diesel or n-butanol, this time under transient conditions of acceleration [50] or starting [51]. Similarly,
review papers appeared recently originating from the present laboratory concerning the exhaust emissions of diesel engines operating under transient conditions with bio-diesel diesel fuel blends
[52,53], and with ethanol or n-butanol diesel fuel blends [54].
Filling an obvious gap of the relevant literature, the present
work presents a vis--vis study when vegetable oil (cottonseed),
its derived methyl ester bio-diesel, ethanol and n-butanol are used
in blends with diesel fuel in the same turbocharged, HDDI,
Mercedes-Benz diesel engine, under the same steady-state operating conditions. This work is conducted along the lines of a similar
very recently appeared work when vegetable oil (cottonseed), its
derived methyl ester bio-diesel, ethanol, n-butanol and diethyl
ether (DEE) were used in blends with diesel fuel, this time in the
same, single-cylinder, four-stroke, water-cooled, Ricardo/Cussons,
Hydra, high-speed direct injection (HSDI), experimental diesel
standard engine, under the same operating conditions [4]. To the
authors knowledge, this is the rst time that such a comparison
is reported for many bio-fuels diesel fuel blends in a turbocharged,
HDDI engine, actually for the above four most commonly used biofuels, under steady-state conditions. What is more, the comparison
is extended to transient conditions under various representative
acceleration schedules, for cottonseed bio-diesel and n-butanol in
blends with diesel fuel on the same engine. A comparison is made
of the main regulated emissions of smoke and nitric oxide (NO)
with the steady-state ones, of course under the recognition of the
highly different non-fuel factors (see above) affecting the transient
operating schedules, trying to de-convolute the inuence of the
differing bio-fuels properties among themselves and those of the

neat diesel fuel.
Specically for the steady-state conditions, the comparative
evaluation is carried out on a common solid basis (engine and
operating conditions) concerning combustion and all regulated
emissions (smoke, NOx, CO, HC) characteristics of blends in diesel
fuel of cottonseed oil, its bio-diesel, and the two (lower) alcohols.
This is founded on the results of experimental heat release analysis
of the acquired fuel injection pressure, and the cylinder pressure
diagrams producing gross heat release rates and mean gas temperatures, which reveal interesting features of bio-fuels blends combustion and emissions formation. The comparison is effected
with the use of the fuel-bound oxygen in the blend as the main
common variable, which is a parameter known to strongly inuence the combustion behavior via the local fuelair ratio in the various zones and, hence, the temperatures and emissions formation
[4]. The rest of the important properties of the bio-fuels blends,
such as mainly bulk modulus (of elasticity), lower heating value
(LHV), kinematic viscosity and latent heat of evaporation are used
to interpret the experimental ndings, given that they attain by
necessity different values for the same value of the fuel-bound
oxygen in the blend, so that drawing useful conclusions as to their
impact on combustion and emissions on top of that of the fuelbound oxygen in the blend. These can be proved also useful for
interpreting the emissions-wise behavior under the transient operating conditions, taking also into account the different non-fuel
factors inuencing the transient operating schedules.
2. Experimental test bed installation
2.1. Engine
Facilities to monitor and control engine variables were installed
on a test-bed, Mercedes-Benz OM 366 LA, six-cylinder, heavyduty direct injection (HDDI), four-stroke, water-cooled, diesel
engine located at the authors laboratory. The engine is turbocharged with a Garrett TBP 418-1 waste-gate turbocharger
and an air-to-air after-cooler. It is widely used to power medium
trucks and mini-buses. It is coupled to a Schenck U1-40 hydraulic
brake (dynamometer), which is a variable ll brake, which allows a
good simulation of a vehicles acceleration.
The static injection timing of the engine is reduced up to a value
of 5 CA (Crank Angle) before TDC (Top Dead Center) at high loads,
for the purpose of reducing nitrogen oxides emissions to meet the
Euro II emission standards. Moreover, it possesses a fuel limiter
(cut-off) device, which is practically an aneroid device controlling
the fuel pump rack maximum travel according to boost pressure,
in order to limit the exhaust smoke level during demanding conditions, such as heavy transients or low-speed, high-load, steadystate operation. The basic data for the engine, injection system
and turbocharger are shown in Table 1. Fig. 1 provides a full schematic arrangement of the engine test bed, instrumentation and
data logging system, with the exemption of the steady-state
exhaust gas analyzers for not impairing its clarity.
2.2. Measurement of emissions
Concerning the steady-state emission measurements, the
exhaust gas analysis system consisted of a group of analyzers for
measuring soot (smoke), nitrogen oxides (NOx), carbon monoxide
(CO) and total unburned hydrocarbons (HC). The smoke level in
the exhaust gas was measured with a Bosch RTT-100 opacimeter,
the readings of which are provided as smoke opacity in % Hartridge
units, or equivalent smoke (soot) density (milligrams of soot per
cubic meter of exhaust gases). The nitrogen oxides concentration
Table 1
Engine, injection system, and turbocharger basic data.
Engine model and type
Mercedes-Benz, OM 366 LA, 6-cylinder, in-line,

4-stroke, compression ignition, direct injection,
water-cooled, turbocharged, after-cooled, with
bowl in piston
Speed range
Engine total displacement
Bore/stroke
Connecting rod length
Compression ratio
Firing order
Maximum power
Maximum torque
Inlet valve opening
Inlet valve closure
Exhaust valve opening
Exhaust valve closure
Fuel pump
8002600 rpm
5958 cm3
97.5 mm/133 mm
230 mm
18:1
15-36-24
177 kW at 2600 rpm
840 Nm at 12501500 rpm
15 crank angle before Top Dead Center
25 crank angle after Bottom Dead Center
68 crank angle before Bottom Dead Center
12 crank angle after Top Dead Center
Bosch PE-S series, in-line, 6-cylinder, with fuel
limiter, and Bosch variable-speed mechanical
governor
5 1 degrees crank angle before Top Dead Center
(at full load)
Bosch, with ve injector nozzle holes and
opening pressure of 250 bar
Garrett TBP 418-1 with internal waste-gate
Air-to-Air
Exhaust
Filter
Filter
Keithley
Data Acquisition Card
Cambustion
CLD 500
fast NO
analyzer
AVL 439
fastresponse
Opacity
meter
40
30
20
10
0
0
Shaft encoder (engine

speed, crank angle)
Fuel pump
rack position
90
180 270 360
Tektronix
Oscilloscope
Exhaust
Exhaust
Temperature Pressure
Amplifier
Fuel tank
Cylinder
pressure
To Data
Acquisition Card
PC Control
Panel
60
50
After-turbo line
Cylinder exhaust line
in ppm (parts per million, by vol.) in the exhaust was measured

with a Signal Series-4000 chemiluminescent analyzer (CLA) and
was tted with a thermostatically controlled heated line. The CO
00
Turbocharger
After-cooler
Injector body and nozzle
Static injection timing
concentration (in ppm) in the exhaust was measured with a

Signal Series-7200 non-dispersive infrared analyzer (NDIR)
equipped with a Signal Series-2505 M Cooler. The total unburned
hydrocarbons concentration (in ppm) in the exhaust was measured
with a Ratsch-Instruments Series RS55 ame-ionization detector
(FID) and was also tted with a thermostatically controlled heated
line.
For the continuous measurement of nitric oxide (NO) emissions
in the exhaust gas demanded under the transient condition tests
(accelerations), the ultra-fast response analyzer CLD500 by
Cambustion Ltd. was employed. This is a chemiluminescent detector (CLD) used for measuring NO and NOx (in the latter case incorporating a NO2 to NO converter) concentration in the exhaust gas,
with a 9010% response time of approximately 2 ms for NO and
10 ms for NOx. These very short response times are achieved by
locating the detectors in remote sample heads, which are positioned very close to the sample point in the engine, and by conveying the sample gas to the detectors under the inuence of a
vacuum through narrow heated capillaries. The linearity of the
analyzer is less than 1% FSO (full scale output), its drift is less than
1% FSO per hour and its accuracy is 5 ppm. Only NO concentration
was selected to be measured, owing to the very low values of NO2/
NOx ratio generally experienced in diesel engines, particularly at
the conditions encountered during abrupt transients.
For the continuous measurement of exhaust gas (smoke) opacity demanded under the transient condition tests (accelerations),
the AVL 439 partial ow Opacimeter was used. This is a device particularly suitable for dynamic testing measurements, with the
Boost Pressure
Turbocharger T/C
Speed A/C
LVDT
Fuel Pump
Mercedes-Benz OM 366 LA
Hydraulic Dynamometer
Fig. 1. Schematic arrangement of the engine test bed installation, instrumentation, and data acquisition system (steady-state gas analyzers not shown for clarity).
exhaust gas sample owing continuously through the opacimeter

with constant ow rate. The response time of the opacimeter is less
than 0.1 s and its accuracy is 0.1% opacity. The opacity of the sample is determined from the measurement of the attenuation of visible light by the smoke in the exhaust gas sample located between
the light source and the detector unit. The opacimeter outputs the
measurement either in terms of opacity values (0100%), as in the
case of the present study, or absorption coefcient values (0
10 m 1). Its technical characteristics comply with legal requirements such as ECE R24, SAE J 1667 and the ELR test cycle, with
the respective lter algorithms pre-programmed into the opacimeter. Here, no lter algorithm was applied (raw signal) in order to
capture successfully all the smoke emission peaks, with no loss of
information. The location of sampling and return lines, as seen in
Fig. 1, is downstream of the turbocharger.
2.3. Measurement of engine and turbocharger operating parameters

Inlet and exhaust pressures and temperatures at various strategic locations were measured during steady-state conditions with
conventional analogue devices, together with fuel consumption
measurements using a gravimetric fuel tank (not used in this
study). Table 2 shows the accuracy of the measurements including
those of the exhaust gas analyzer modules used for the steadystate tests. For measuring the pressure in one of the cylinders, a
Kistler miniature piezoelectric transducer was used, mounted to
the cylinder head and connected to a Kistler charge amplier.
Also, a Kistler piezoelectric transducer connected to a Kistler
charge amplier was used, tted on the injector side of the pipe
linking the injection pump and injector, in order to provide the fuel
pressure signal. The pressures from the transducers are measured
with accuracy better than 1% FSO. The heat release analysis of
the experimentally obtained combustion chamber (cylinder) pressure diagrams is outlined in a later section.
The engine and turbocharger operating parameters measured
and recorded continuously, during the transient tests, were: engine
speed, cylinder pressure, fuel pump rack position, boost pressure,
and turbocharger speed. The location of each measuring device
on the experimental test bed installation is shown in Fig. 1.
Table 3 provides a brief list of the various measuring devices
Table 2
Accuracy of measurements (steady-state conditions).
Measurements
Accuracy
Smoke opacity
NOx
CO
HC
Speed
Torque
0.1%
5 ppm
2 ppm
0.5 ppm
2 rpm
0.5 Nm
Table 3
Measuring devices for the engine and turbocharger operating parameters and their
measuring error (transient conditions).
Parameter
Measuring device
Error
Engine speed
Cylinder pressure
Kistler shaft encoder

Kistler miniature piezoelectric
transducer, combined with Kistler
charge amplier
Linear Variable Differential
Transducer (LVDT)
Wika pressure transmitter
Garrett turbo speed sensor
(including gauge)
0.02 CA
<1% FSO
Fuel pump rack position

Boost pressure
Turbocharger speed
0.1 mm
<1% FSO
0.5% FSO
together with their measuring error, while more details can be

found in Ref. [55]. A custom made stop with various adjustable
positions, each one corresponding to a specic engine speed, was
tted on the (accelerator) pedal in order to ensure constant pedal
position at the end of each acceleration test as well as repeatability
of the accelerations.
2.4. Data acquisition and processing system
All the above mentioned signals from the measuring devices
and instruments are fed into the input of the data acquisition module, which is a Keithley KUSB 3102 ADC card connected to a
Pentium Dual Core PC via USB interface. The specic card has a
maximum sampling rate of 100 ksamples/s, with a 12-bit resolution for its 8 differential analogue inputs, and the accuracy of the
analogue input readings of the data acquisition system is within
0.01%. Following the storage of the recorded measurements into
les of an IBM compatible Pentium IV PC, the data were processed
using in-house developed computer codes.
3. Properties of fuels tested, mixing, and selection of blending
ratios
The conventional diesel fuel was supplied by Aspropyrgos
Reneries of the Hellenic Petroleum SA, representing the typical,
Greek automotive, low sulfur (0.035%) diesel fuel (gasoil).
The vegetable oil used was cottonseed oil, from which its
(methyl-ester, ME) bio-diesel was produced via the transesterication process. These bio-fuels were mixed by stirring with the conventional diesel fuel at blending ratios of 10/90 and 20/80 (by vol.),
noting that these blends do not separate after mixing. The cottonseed oil used was obtained from Greek commercial processing
facilities. It was rened and de-gummed, very nearly the edible
type, without any additive and preheating to reduce its viscosity.
The derived cottonseed bio-diesel used was supplied from and produced at the Chemical Process Laboratory of the School of Chemical
Engineering, of the National Technical University of Athens, via
transesterication with methanol of the corresponding feedstock
raw material at a Pilot Plant using potassium hydroxide (KOH) as
catalyst. The product was tested according to the EN 14214 standards [56].
The ethanol of 99% purity was purchased from local commercial
representatives, and was blended with the normal diesel fuel at
blending ratios of 5/95 and 10/90 (by vol.). No cetane improving
additives (ignition improvers) were used. An emulsifying agent
by Betz GE, a division of General Electric Inc., was used in proportions of 1.5% (by vol.), to satisfy mixture homogeneity and prevent
phase separation. The mixing protocol consisted of rst blending
the emulsier into the ethanol and then blending this mixture into
the neat diesel fuel. The isomer of butanol, n-butanol, was used in
the present study. It was purchased from local commercial representatives certied to a purity of 99.9% (analytical grade), and
was blended with the normal diesel fuel at blending ratios of 8/
92 and 16/84 (by vol.). Preliminary evaluation tests on the solubility of n-butanol in the diesel fuel with blending ratios up to 50/50
proved, actually, that the mixing was excellent with no phase separation at all for a period of several days, as was ascertained by
monitoring glass burettes containing these fuel blends. Then, no
emulsifying agent was necessary in this case. For blending all the
above fuels, a mild stirring with a small paddle for a couple of minutes was sufcient.
The properties of the diesel fuel, the cottonseed oil, its biodiesel, the ethanol, and the n-butanol are summarized in Table 4.
Only the density and lower caloric values were used in the computations, with all the other cited properties referred to here for
Table 4
Properties of diesel fuel, cottonseed oil, cottonseed (methyl ester) bio-diesel, ethanol, and n-butanol.
Fuel properties
3
Density at 20 C (kg/m )
Lower caloric value (kJ/kg)
Kinematic viscosity at 40 C (mm2/s)
Cetane number
Bulk modulus of elasticity (bar)
Boiling point (C)
Latent heat of evaporation (kJ/kg)
Stoichiometric airfuel ratio
Oxygen (% by weight)
a
Diesel fuel
Cottonseed oil
Cottonseed bio-diesel
Ethanol
n-Butanol
825
43,000
2.6
50
16,000
180360
250
15
0
910
36,780
34
38
19,000
340480
210
12.5
10
885
37,500
4
52
17,500
280400
230
12.5
10
788
26,800
1.2
8
13,200
78
840
9.0
34.8
810
33,100
3.6a
25
15,000
118
585
11.2
21.6
Measured at 20 C.
comparative purposes, in order to explain qualitatively the relative

combustion and emissions behavior of the different fuels blends.
Selection of low blending ratios for ethanol or n-butanol was
dictated by the necessity to avoid any cyclic combustion irregularity phenomena, which may appear in diesel engines when very low
cetane number fuels (cf. values in Table 4) are used [4]. The rationale for selecting the specic blending ratios with diesel fuel, i.e. of
5/95 and 10/90 for ethanol as against 8/92 and 16/84 for n-butanol,
is that 5% ethanol and 8% n-butanol in the blend gives almost the
same percentage of fuel-bound oxygen in the blend (cf. their oxygen contents in Table 4), and the same holds true for the 10% ethanol and 16% n-butanol in the blend. On the other hand, the
blending ratios for either vegetable oil or bio-diesel selected of
10/90 and 20/80 are the most usual and recommended ones.
This way, the comparison of the corresponding blends for ethanol and n-butanol is effected on the premise of an almost equal
parameter, which is known to strongly inuence the combustion
behavior, via the local fuelair ratio in the various zones and,
consequently, the temperatures and emissions formation.
Meanwhile, the bracketed corresponding values for the cottonseed
oil and its bio-diesel help to draw related useful conclusions, as
will be revealed by the structure of the diagrams to be presented
later in the Results sections. To be noted that the air aspirated by
the engine is constant for the same load and speed conditions. Of
course, other parameters such as mainly viscosity, cetane number,
caloric value, and latent heat of evaporation do not attain then (in
general) equal values. To be noted that the C/H atom ratios for the
diesel fuel, the vegetable oil and its bio-diesel are (in the vicinity
of) 2, for the ethanol 3, and for the n-butanol 2.5. It correlates with
density and viscosity, but its effect on combustion is expected to be
obscured here by the presence of oxygen in bio-fuels.
The previously mentioned selection of blends concerned only
the steady-state measurements. Owing to the complexities and difculties of the transient tests conducted, only two blends were
selected and experimented with, viz. a blend of 30% (by vol.) biodiesel with diesel fuel and one of 25% (by vol.) n-butanol with diesel fuel. For the other two bio-fuels there were no transient tests
conducted, as the vegetable oil might have caused blocking of
the thin pipes incorporated in the transient exhaust gas analyzers
and the possible blend separation when using ethanol. The use of
higher blending ratios of both bio-fuels with the conventional diesel fuel was selected for the differences to be more prominent and
the underlying mechanisms better understood.
4. Parameters tested and experimental procedure

4.1. Steady-state tests
The series of tests were conducted using each of the above mentioned blends, with the engine working at speeds of 1200 and
1500 rpm, and at three loads of 20%, 40% and 60% of the full load,
corresponding to brake mean effective pressures (b.m.e.p.) of 3.56,
7.04 and 10.52 bar, respectively. Owing to the differences among
the caloric values and oxygen contents of the fuels tested, the
comparison was effected at the same engine brake mean effective
pressure (load) and not at the same injected fuel mass or air-tofuel ratio. In each test, exhaust smokiness and exhaust regulated
gas emissions such as nitrogen oxides, carbon monoxide and total
unburned hydrocarbons were measured. At the same time, during
each test, combustion chamber (indicator) and fuel injection pressure diagrams were obtained using the data acquisition system
described above. The heat release analysis of these experimentally
obtained cylinder pressure diagrams is outlined in the next section.
The experimental work started with a preliminary investigation
of the engine fueled with neat diesel fuel in order to determine the
engine operating characteristics and exhaust emission levels, constituting the baseline, which is compared with the corresponding
cases when using the bio-fuels/diesel fuel blends. The same procedure was repeated for each fuel blend by keeping the same operating conditions. For every fuel change, the fuel lines were cleaned
and the engine was left to operate for about 30 min to stabilize
at its new desired condition.
For each engine operating point and fuel blend the measurements were repeated three times, with the reported values being
the mean ones. The coefcient of variation COV (standard deviation divided by the mean value) for all reported quantities was
determined at a maximum of 3%, which indicates that the measurements were quite repeatable.
4.2. Transient tests
The experimental matrix included various cases of acceleration,
given that the engine is intended for automotive applications.
Since the engine is coupled to a hydraulic dynamometer, during
all acceleration cases the brake load (resistance) increased accordingly. This is actually the case when a vehicle accelerates in realworld driving conditions, i.e. the increase in engine/vehicle speed
results in an increase of both tire rolling and aerodynamic resistance. In all test cases, the engine was allowed to stabilize at the
initial steady-state condition and then the pedal was pushed to
the end of the adjustable custom made stop to accelerate the
engine.
The acceleration tests were performed for various combinations
of initial engine speed and load, mimicking vehicle real accelerations under various (vehicle) speeds and gears, with the details
given in Table 5. Also, Fig. 2 provides an illustration of the initial
and nal conditions of each conducted test in a speed-load graph.
Initially, all tests were conducted with the engine running on
neat diesel fuel, constituting the baseline to which the corresponding cases are compared when using the blends of diesel with
bio-diesel or n-butanol. The same tests were performed for each

Table 5
Tabulation of the transient test conditions (accelerations) examined.
Test No.
Initial conditions
1.
2.
3.
Final conditions
Speed (rpm)
Load (%)
Speed (rpm)
Load (%)
1016
1530
1530
10
10
40
1880
2080
2055
15
20
75
Properties of the cylinder content are provided as fourth order

polynomial expressions of the absolute temperature [61]. The
equations of the thermodynamic model are solved numerically
step-by-step using a simple time marching technique. The differential equations are converted into algebraic ones using a simple
Euler scheme.
6. Presentation and discussion of steady-state results

80
6.1. Combustion heat release analysis results

Test 3
Load (%)
60
40
Test 2
20
Test 1
0
800
1200
1600
2000
2400
Engine Speed (rpm)

Fig. 2. Illustration of initial and nal conditions of each transient test examined.
fuel blend (described previously) assuring the best possible

repeatability, via the custom made stop tted on the accelerator
pedal. For every fuel change, the fuel lines were cleaned and the
engine was left to run for a sufcient period of time to stabilize
at its new condition. Additionally, a preconditioning procedure
was followed between each fuel change in order to remove the
deposited particulate matter on the exhaust pipe walls, which
could be blown out and released during the following tests [57],
hence leading to faulty measurements of smoke opacity and erroneous interpretations for each fuel blend.
5. Outline of experimental heat release analysis
The method of processing the experimental cylinder pressure
diagrams and their analysis for heat release has been reported in
detail in previous publications by the authors, as for example in
[19]. A recording was made of the cylinder (indicator) pressure
data for ten cycles in a contiguous le, with a sampling rate corresponding to 0.5 CA. Then, the mean of the cylinder (indicator)
and the fuel pressure diagrams are obtained, and a light smoothing for the pressure signals is applied based on performing a sixdata points weighted smoothing.
The measured pressure data processed for the heat release analysis concern the closed part of the thermodynamic cycle. A spatial
uniformity of pressure, temperature and composition in the combustion chamber (single-zone model), at each instant of time or
during a crank angle step or instantaneous cylinder volume, is
assumed [58]. By combining the rst law of thermodynamics and
the perfect gas state equation in differential form for the cylinder
gas content, the net heat release rate dQn/du (with respect to crank
angle u) is derived [59].
Thus, the corresponding gross heat release rate dQg/du, which is
the energy released from the combustion of fuel, is given by the
sum of dQn/du and dQw/du, with the latter standing for the rate
of heat transferred to the combustion chamber walls, calculated
by using the formula of Annand [60].
In this subsection, results are presented in the four subgures of

Figs. 3 and 4 for the 20% load (b.m.e.p. = 3.56 bar), 40% load
(b.m.e.p. = 7.04 bar), and 60% load (b.m.e.p. = 10.52 bar) cases, for
the neat diesel fuel and its blends with 20% (by vol.) cottonseed
oil (VC20-D) or 20% of its methyl ester bio-diesel (BC20-D) in
Fig. 3, and for the neat diesel fuel and its blends with 10% of ethanol (ET10-D) or 16% of n-butanol (BU16-D) in Fig. 4. This is dictated, on the one hand, for the sake of brevity of space of this
paper and, on the other, by the differences in the respective diagrams that are relatively better discernible in the cases of the highest percentages of the various bio-fuels in the blend. Similarly, for
the sake of brevity, results are presented only at the engine speed
of 1200 rpm. The position of hot TDC (Top Dead Center) in these
diagrams corresponds to 180 CA.
It is understood that one might have expected inclusion of all
four bio-fuels blends in a single gure, i.e. merging of Figs. 3 and
4, but this is prohibited owing to jamming of too many curves.
However, the corresponding subgures (ad) will be discussed in
the following vis--vis.
Fig. 3a shows, for the speed of 1200 rpm at the three loads considered, the fuel (injection) pressure against crank angle diagrams,
for the neat diesel fuel and its blends with 20% cottonseed oil or
20% of its bio-diesel, while counterpart Fig. 4a shows the same
information for the neat diesel fuel and its blends with 10% ethanol or 16% n-butanol. First it can be seen, as expected, that the
injection duration increases with engine load for the neat diesel
fuel and all four bio-fuels blends, and the same holds true for
the injection pressures. Note that in the case of high load, the
residual fuel pressure in the connecting pipeline is lower, a fact
attributed to the particular functioning of the present injection
pump system that is forced to have then a much delayed pump
spill timing (static injection) for NOx reduction, as mentioned in
Section 2. The noticeable high displacement at the high load of
the injection pulse is obviously attributed to that deliberate delay
of static injection timing.
It can be observed that for all loads considered, the fuel pressure
diagrams for the cottonseed oil or its bio-diesel diesel fuel blends
against the corresponding ones with neat diesel fuel (Fig. 3a) do
not show any appreciable differences in injection duration or maximum pressure, and this also holds true for their uprising leg (i.e.
the rst abrupt rise in pressure part) that dictates the dynamic
injection timing. The corresponding fuel pressure diagrams for
the ethanol or n-butanol diesel fuel blends against the corresponding ones with neat diesel fuel (Fig. 4a) do not show again any
appreciable differences in injection duration or maximum pressure. For the two lower loads the injection pulse has almost the
same shape for the ethanol or n-butanol diesel fuel blends against
the corresponding neat diesel fuel cases, unlike the high load case
where an hesitant hump (i.e. after the rst rise in pressure, the
pressure rise seems to mitigate a bit and then recover) is observed
with the ethanol or n-butanol diesel fuel blends. All ethanol or nbutanol diesel fuel blends diagrams show a similar size slight displacement with respect to the corresponding ones with neat diesel
fuel, hence presenting delayed dynamic injection timings.
(b) 100
VC20-D, 20% load
VC20-D, 40% load
VC20-D, 60% load
BC20-D, 20% load
BC20-D, 40% load
BC20-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
1200 rpm
Fuel pressure (bar)
600
400
1200 rpm
80
Cylinder pressure (bar)
(a) 800
60
VC20-D, 20% load
VC20-D, 40% load
VC20-D, 60% load
BC20-D, 20% load
BC20-D, 40% load
BC20-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
40
200
20
TDC
0
160
TDC
180
200
160
220
Degrees crank angle
VC20-D, 20% load

VC20-D, 40% load
VC20-D, 60% load
BC20-D, 20% load
BC20-D, 40% load
BC20-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
1200 rpm
80
40
TDC
170
180
190
1200 rpm
1600
1200
TDC
400
200
220
(d) 2000
800
200
Degrees crank angle
Temperature (K)
Gross heat release rate (J/deg.)
(c) 120
180
210
220
230
Degrees crank angle
160
VC20-D, 20% load

VC20-D, 40% load
VC20-D, 60% load
BC20-D, 20% load
BC20-D, 40% load
BC20-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
180
200
Degrees crank angle
220
Fig. 3. Fuel (injection) pressure (a), cylinder pressure (b), gross heat release rate (c), and cylinder temperature (d), against crank angle diagrams for the neat diesel fuel and its
blends with 20% cottonseed oil (VC20-D) or 20% of its bio-diesel (BC20-D), for the three loads at 1200 rpm.
The behavior of the fuel pressure diagrams is attributed to the

different densities ql and bulk moduli of elasticity Kbm of the fuels
tested inuencing the whole injection process, while the static
injection timing (at pump spill) is kept constant. The relevant
behavior is explained qualitatively in detail in [62], where the simplied analysis of Obert [63] is followed. The whole phenomenon
depends on the speed of sound as = (Kbm/q)1/2 with which the fuel
pressure waves propagate inside the fuel pump-injector connecting pipeline. Using the relevant values in Table 4, the speed of
sound as takes descending values in the order: vegetable oil
1445 m/s, bio-diesel 1406 m/s, diesel fuel 1392 m/s, n-butanol
1361 m/s, and ethanol 1294 m/s. The small injection advancement
expected with 100% vegetable oil or bio-diesel against the neat diesel fuel case [64] is of the order less than 1.0 CA. Thus, for the present investigation with 20% cottonseed oil or bio-diesel blends and
assuming in approximation linearity, any existing difference
should not be well discernible (given the resolution of 0.5 CA for
the present diagrams), and hence not expected to inuence the
combustion behavior (for the same load). On the contrary, the values of the injection delay expected for the corresponding cases of
the ethanol [65] or n-butanol diesel fuel blends are slightly
discernible.
Figs. 3b and 4b show the corresponding cylinder pressure

against crank angle diagrams, focusing on their part around TDC.
First it can be seen, as expected, that the pressures increase with
load for all fuels, while the compression lines increase with load
due to the turbocharger action.
In Fig. 3b, it is seen that the pressure rise (due to combustion)
practically starts at the same point for the cottonseed oil diesel fuel
blend and the corresponding neat diesel fuel case (for the same
load). Given the above mentioned identical initiation of fuel injection, this behavior might appear strange for the cottonseed oil
blend considering its lower cetane number (cf. values in Table 4).
This is possibly attributed to the usual Cetane Number
Measuring Method (developed for diesel fuels) under-rating the
self-ignition characteristics of vegetable oils, as explained for
example in Ref. [66], while it should also be taken into account
the small percentage of vegetable oil in the blend. All cottonseed
oil blend diagrams show slightly lower maximum pressures with
respect to the corresponding ones with neat diesel fuel. This
behavior may then be attributed to the fuel spray containing
now vegetable oil droplets of bigger size [62,64] that are delayed
to burn (poorer atomization/evaporation due to higher viscosity,
cf. values in Table 4), despite the counteracting effect of the fuel-
(b)
ET10-D, 20% load
ET10-D, 40% load
ET10-D, 60% load
BU16-D, 20% load
BU16-D, 40% load
BU16-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
1200 rpm
Fuel pressure (bar)
600
400
200
100
1200 rpm
80
Cylinder pressure (bar)
(a) 800
60
ET10-D, 20% load
ET10-D, 40% load
ET10-D, 60% load
BU16-D, 20% load
BU16-D, 40% load
BU16-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
40
20
TDC
160
180
200
Degrees crank angle
(c) 120
Gross heat release rate (J/deg.)
80
160
220
ET10-D, 20% load

ET10-D, 40% load
ET10-D, 60% load
BU16-D, 20% load
BU16-D, 40% load
BU16-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
1200 rpm
TDC
180
200
Degrees crank angle
1200 rpm
1600
1200
40
800
TDC
0
170
180
190
200
210
Degrees crank angle
TDC
400
220
230
220
(d) 2000
Temperature (K)
160
ET10-D, 20% load

ET10-D, 40% load
ET10-D, 60% load
BU16-D, 20% load
BU16-D, 40% load
BU16-D, 60% load
Diesel, 20% load
Diesel, 40% load
Diesel, 60% load
180
200
Degrees crank angle
220
Fig. 4. Fuel (injection) pressure (a), cylinder pressure (b), gross heat release rate (c), and cylinder temperature (d), against crank angle diagrams for the neat diesel fuel and its
blends with 10% ethanol (ET10-D) or 16% n-butanol (BU16-D), for the three loads at 1200 rpm.
bound oxygen, by noting also the rather low temperature environment for this engine as operating with retarded injection timings.
Again in Fig. 3b, it is seen that the pressure rise practically starts at
the same point for the cottonseed bio-diesel diesel fuel blend and
the corresponding neat diesel fuel case (for the same load). This is
attributed to the above mentioned identical initiation of fuel injection, while there is no appreciable difference in their ignition delay
values as having almost the same cetane number (cf. values in
Table 4). All cottonseed bio-diesel blend diagrams show slightly
lower maximum pressures (of similar size to the cottonseed oil
blends) with respect to the corresponding ones with neat diesel
fuel. The explanation for this behavior is the same as the one given
above for the corresponding cottonseed oil blends, since again the
fuel spray contains bio-diesel droplets of bigger size.
In Fig. 4b, it is seen that all ethanol or n-butanol diesel fuel
blend diagrams show (similar size) lower maximum pressures
with respect to the corresponding ones with neat diesel fuel, a fact
attributed to the delayed combustion with these blends. The latter
is owed to the delayed dynamic injection timing mentioned above
and to the higher ignition delay due to their lower cetane number
(cf. values in Table 4). The combination of relatively higher values
of delayed dynamic injection timing and lower cetane number of
ethanol or n-butanol against cottonseed oil or its bio-diesel, contributes to their maximum pressures being correspondingly lower
(cf. Figs. 3b and 4b).
Figs. 3c and 4c show the corresponding gross heat release rate
First it can be seen, as expected, that the heat release rate values
increase with load for all fuels. For the lower load, both parts of
combustion, i.e. the premixed combustion (the part under the rst
peak) and the diffusion combustion (the last part under the second more rounded peak) are apparent, but with the diffusion
combustion possessing a minor role. For the higher loads, the premixed combustion part tends to disappear with the diffusion combustion prevailing.
In Fig. 3c, it is seen that all cottonseed oil or cottonseed biodiesel blend diagrams show (similar size) slight delay on their falling leg with respect to the corresponding ones with neat diesel
fuel. This corroborates the above mentioned argument, with reference to Fig. 3b, that the fuel spray contains now vegetable oil or
bio-diesel droplets of bigger size [62,64] that are delayed to burn.
In Fig. 4c, it is seen that for the 20% load the premixed combustion peak for the ethanol or the n-butanol diesel fuel blends is
higher and sharper against the corresponding neat diesel fuel case,
6.2. Emissions results

The gures to follow in this subsection, provide each emission
parameter for the neat diesel fuel and its blends with 10% and
20% (by vol.) cottonseed oil (VC), with 10% and 20% of its bio-diesel
(BC), with 5% and 10% ethanol (ETH), and with 8% and 16% n-butanol (BUT), at the three loads considered, separately at the engine
speeds of 1200 and 1500 rpm. Soot (smoke), nitrogen oxides (NOx),
carbon monoxide (CO) and total unburned hydrocarbons (HC)
exhaust emissions are presented in Figs. 512, respectively. To
effect comparison between cottonseed oil, its derived bio-diesel,
ethanol, and n-butanol diesel fuel blends, these diagrams have as
independent (abscissa values) variable the fuel-bound oxygen in
the fuel blend (% by weight). One can remark the almost equal values of this important variable concerning ethanol and n-butanol
blends, while the ones for cottonseed oil and its derived bio-diesel
14
Speed
1200 rpm
Smoke Opacity (% Hartridge)
whereas for the 40% load it is not well discernible for the ethanol
blend and better discernible for the n-butanol blend. It is the lower
cetane number of ethanol or n-butanol (cf. values in Table 4) that
causes the increase of ignition delay and so the increased amount
of prepared fuel (to this end may also assist the easier evaporation) for combustion after the start of ignition. However, as noticed
in Fig. 3b, this is translated into lower maximum pressures, probably because of the more than offsetting effect of later combustion
into a lower temperature environment. The displacement (delay)
of the ethanol or n-butanol against cottonseed oil or its bio-diesel
heat release rate diagrams is apparent due the relatively higher
ignition delay discussed above (cf. Figs. 3c and 4c).
Figs. 3d and 4d show the corresponding cylinder temperature
First it can be seen, as expected, that there is a temperature
increase with load for all fuels.
In Fig. 3d, it is seen that all cottonseed oil or cottonseed biodiesel blend diagrams show (similar size) slightly lower maximum
temperatures, with respect to the corresponding ones with neat
diesel fuel. This accords with the above mentioned argument, with
reference to Fig. 3c, that the fuel spray contains now vegetable oil
or cottonseed bio-diesel droplets of bigger size that are delayed to
burn. It is stated, however, that this is a computed mixed mean
temperature due to the inherent single-zone modeling assumptions of the heat release analysis followed, so that these results
should be interpreted with caution. Nonetheless, the shown mean
temperature differences in the order of 30 degrees (and so much
higher on a local basis in a heterogeneous diesel combustion environment) may be critical, especially for NOx formation when
exceeding a certain temperature threshold.
In Fig. 4d, it is seen that all ethanol or n-butanol blend diagrams
show (similar size) lower maximum temperatures, with respect to
the corresponding ones with neat diesel fuel. One can observe that
for each load considered, the temperatures for the blends are
slightly displaced due to the delayed start of combustion mentioned above, being for the rst part of combustion (20 to 30
CA) lower than the corresponding ones for the neat diesel fuel case
while leveling off later. Actually, as reported in [67], measured incylinder temperatures during the combustion stage showed much
lower temperatures for the case of a 15% (by vol.) ethanol in diesel
blend. The same situation is expected to hold true for n-butanol
too, most likely at a lesser extent. The single-zone modeling
assumption rounds these results, although it manages to capture
qualitatively correctly this mechanism. The combination of relatively lower values of maximum pressures and higher delayed
dynamic injection timings (injection into a lower temperature
environment) of ethanol or n-butanol against cottonseed oil or
its bio-diesel, contributes to their maximum temperatures being
correspondingly lower (cf. Figs. 3d and 4d).
Bio-fuel
ETH
BUT
BC
VC
12
b.m.e.p.=10.52 bar
10
8
b.m.e.p.=7.04 bar
4
b.m.e.p.=3.56 bar
2
0
1
2
3
4
Fuel-bound oxygen in fuel blend (% by wt.)
Fig. 5. Emitted (soot) smoke opacity (% Hartridge) as a function of fuel-bound

oxygen in the fuel blend, for the neat diesel fuel and its various blends with
cottonseed oil (VC), its bio-diesel (BC), ethanol (ETH), and n-butanol (BUT), for the
three loads (b.m.e.p.) at 1200 rpm.
7
Speed
1500 rpm
10
b.m.e.p.=10.52 bar
Bio-fuel
ETH
BUT
BC
VC
b.m.e.p.=7.04 bar
4
b.m.e.p.=3.56 bar
3
0
1
2
3
4
Fig. 6. Emitted (soot) smoke opacity (% Hartridge) as a function of fuel-bound

oxygen in the fuel blend, for the neat diesel fuel and its various blends with
cottonseed oil (VC), its bio-diesel (BC), ethanol (ETH), and n-butanol (BUT), for the
three loads (b.m.e.p.) at 1500 rpm.
blends are bracketed by the former ones. This variable inuences

strongly the combustion behavior and consequently the emissions
formation, as discussed at the end of Section 3.
Fig. 5 shows, for the speed of 1200 rpm at the three loads considered, the emitted (soot) smoke opacity (% Hartridge) against
fuel-bound oxygen in the fuel blend (% by weight) diagrams, for
the neat diesel fuel and its blends with 10% or 20% cottonseed
oil, 10% or 20% of its bio-diesel, 5% or 10% ethanol, and 8% or 16
n-butanol, while the counterpart Fig. 6 shows the same information for the speed of 1500 rpm. Both of these gures show that
the soot emitted by all bio-fuels diesel fuel blends is markedly
lower than the one for the corresponding neat diesel fuel case, with
this reduction being higher the higher the percentage of bio-fuel in
the blend, i.e. with increasing fuel-bound oxygen content. This is
attributed to the combustion being now assisted by the presence
of the fuel-bound oxygen even in locally rich zones, which seems
11
Nitrogen Oxides (ppm)
1120
1100
b.m.e.p.=10.52 bar
1060
1040
1020
1180
1160
1140
1120
b.m.e.p.=7.04 bar
1100
1080
1060
Speed
1200 rpm
700
Bio-fuel
ETH
BUT
BC
VC
680
660
640
b.m.e.p.=3.56 bar
620
600
0
1
2
3
4
1080
900
880
860
b.m.e.p.=10.52 bar
840
820
800
840
820
b.m.e.p.=7.04 bar
800
780
760
740
580
Speed
1500 rpm
Bio-fuel
ETH
BUT
BC
VC
560
540
520
b.m.e.p.=3.56 bar
500
0
Fig. 7. Emitted nitrogen oxides as a function of fuel-bound oxygen in the fuel blend,
for the neat diesel fuel and its various blends with cottonseed oil (VC), its bio-diesel
(BC), ethanol (ETH), and n-butanol (BUT), for the three loads (b.m.e.p.) at 1200 rpm.
Fig. 8. Emitted nitrogen oxides as a function of fuel-bound oxygen in the fuel blend,
for the neat diesel fuel and its various blends with cottonseed oil (VC), its bio-diesel
(BC), ethanol (ETH), and n-butanol (BUT), for the three loads (b.m.e.p.) at 1500 rpm.
to dominate over the lower temperatures (where existent) that

render difcult the combustion of the formed soot. Likewise, the
absence of sulfur from the bio-fuels should lead to lower particulate matter (PM) emissions. The cottonseed oil blends seem to
reduce more the smoke emissions compared to the corresponding
cases of cottonseed bio-diesel blends. A similar reduction of smoke
emitted by the corresponding ethanol and n-butanol blends is
observed at small content of fuel-bound oxygen, while at higher
contents (say, more than 1.5% by wt.) the ethanol blends show
superiority in smoke reduction over the n-butanol ones. The positive effect in reduction of smoke by the ethanol blends is more evident at the higher engine loads and speed (cf. Figs. 5 and 6).
Figs. 7 and 8 show the corresponding diagrams of the emitted
nitrogen oxides (NOx) in ppm against fuel-bound oxygen in the
fuel blend. One can observe that the NOx emitted by the cottonseed oil or cottonseed bio-diesel blends are slightly higher than
the ones for the corresponding neat diesel fuel case, with this
increase being higher the higher the percentage of the bio-fuel in
the blend, i.e. with increasing fuel-bound oxygen content. This
may be attributed to the fact that with these blends, the decrease
of the cylinder temperatures favoring NOx mitigation is more than
counteracted by the increase of the fuel-bound oxygen in crucial
zones inside the spray (displacing the airfuel ratio toward stoichiometry and a little to the lean) that favors NOx formation. In
contrast, the NOx emitted by the ethanol or n-butanol blends are
slightly lower than the ones for the corresponding neat diesel fuel
case, with this decrease being higher the higher the percentage of
the bio-fuel in the blend. In this case and by the same token, the
higher decrease of the cylinder temperatures favoring NOx mitigation is not counteracted by the increase of the fuel-bound oxygen
in crucial zones inside the spray. The cottonseed bio-diesel blends
seem to increase more the NOx emissions compared to the corresponding cases of cottonseed oil blends. There is a higher reduction
of NOx emitted by the n-butanol blends over the corresponding
ethanol ones.
carbon monoxide (CO) in ppm against fuel-bound oxygen in the
fuel blend. It is observed that the CO emitted by the vegetable oil
fuel blends are higher and for the rest three bio-fuels blends lower
than the ones for the corresponding neat diesel fuel case, with this
tendency becoming stronger the higher the percentage of the biofuel in the blend. With the exception of the vegetable oil blends,
the others follow the same behavior as the emitted soot by the
engine [13], while for the vegetable oil blends the two-way oxidation reactions of carbon or carbon monoxide into carbon dioxide (a
delicate balance), in the presence of oxygen or other radicals originating from the unburned hydrocarbons [59], seem to be displaced toward lower values of soot (cf. Figs. 5 and 6) and higher
of CO. To provide explanations for the relative behavior among
the four bio-fuels blends is very difcult and possibly out of the
state of the art, reminding additionally that the CO emitted level
in diesel engines is in absolute terms small, a fact unfortunately
rendering the explanation of the relative behavior even more
difcult.
total unburned hydrocarbons (HC) in ppm against fuel-bound oxygen in the fuel blend. It is observed that the unburned HC emitted
by all bio-fuels diesel fuel blends are higher than the ones for the
corresponding neat diesel fuel case, with this tendency becoming
stronger the higher the percentage of the bio-fuel in the blend.
As known, the formation of unburned hydrocarbons originates
from various sources in the diesel engine cylinder, with its
75
70
65
Bio-fuel
60
ETH
BUT
BC
VC
65
b.m.e.p.=7.04 bar
60
55
50
45
Speed
1200 rpm
100
90
b.m.e.p.=3.56 bar
80
70
0
1
2
3
4
Carbon Monoxide (ppm)
b.m.e.p.=10.52 bar
70
80
66
70
85
12
64
62
b.m.e.p.=10.52 bar
60
58
56
54
Bio-fuel
ETH
BUT
BC
VC
65
60
b.m.e.p.=7.04 bar
55
50
45
100
Speed
1500 rpm
90
b.m.e.p.=3.56 bar
80
70
0
1
2
3
4
Fig. 9. Emitted carbon monoxide as a function of fuel-bound oxygen in the fuel

blend, for the neat diesel fuel and its various blends with cottonseed oil (VC), its biodiesel (BC), ethanol (ETH), and n-butanol (BUT), for the three loads (b.m.e.p.) at
1200 rpm.
Fig. 10. Emitted carbon monoxide as a function of fuel-bound oxygen in the fuel
blend, for the neat diesel fuel and its various blends with cottonseed oil (VC), its biodiesel (BC), ethanol (ETH), and n-butanol (BUT), for the three loads (b.m.e.p.) at
1500 rpm.
theoretical study being the harder among all regulated emissions

[58]. The higher HC emissions by all bio-fuels diesel fuel blends
may be attributed to the broadening of the lean spray ame-out
region (due to existence of the fuel-bound oxygen) during the ignition delay, having the dominating inuence. This is the region in
which the fuel is already mixed beyond the lean limit of combustion, without then being able to auto-ignite and sustain a fast reaction front [59]. In any case, it is reminded that the unburned HC
emitted level in diesel engines is in absolute terms small.
In closure, from the results presented in the above two subsections, the belief is strengthened that the choice of equal values of
fuel-bound oxygen in the blends, for comparison of the combustion
process and emissions, was a rational criterion at least in the way
manifested in the single-zone (mixed mean) assumptions of an
experimental heat release rate model. The present analysis is
proved useful for interpreting the relative behavior between the
blends of each bio-fuel against the neat diesel fuel case, unlike
the case of comparison among the various bio-fuels blends that
may be inadequate. The successful treatment of the latter may
require the specic details of the distribution of fuelair ratio
and temperatures inside the cylinder or even the inuence of the
specic structure of the fuels molecule, which falls outside the
capabilities of the present model (and possibly the state of the
art) and the scope of this study.
Smoke NOx trade-off, a really disappointing problem for diesel

engine designers [1,59]. It is then interesting to investigate the
inuence of the various tested bio-fuels blends on this trade-off.
Therefore, Fig. 13 is drawn (using in effect relevant information
from Figs. 58), which shows the emitted smoke (opacity) nitrogen oxides trade-off, for the neat diesel fuel and its various blends
with cottonseed oil, its bio-diesel, ethanol, and n-butanol. It refers
to the engine speed of 1200 rpm and the three examined loads.
Each load case is depicted as a grape bunch, with its peak denoting the corresponding neat diesel fuel case. The small numbers
near the drawing symbols denote the values of fuel-bound oxygen
in the fuel blend, thus covering all the examined proportions of
each bio-fuel in its blends with diesel fuel, with the proportion
increasing as one moves away from the bunch peak.
It is clearly seen that this Smoke NOx trade-off (at each load)
still exists for the cottonseed oil and bio-diesel blends cases (with
increasing proportion in their blend with diesel fuel), with the cottonseed oil blends performing better. On the contrary, for the ethanol and n-butanol blends cases, this trade-off is defeated, i.e. with
increasing proportion of either ethanol or n-butanol (in their blend
with diesel fuel) a simultaneous decrease of smoke and NOx is
effected (at all loads), with the n-butanol blends performing better.
7. Presentation and discussion of transient results and
comparison with steady-state
6.3. Smoke NOx trade-off

As known, for diesel engines operated at a constant load, any
change of a parameter that decreases smoke leads to increase of
NOx emissions and vice versa. This is the notorious so called
The discussion of the results and their interpretation in this section focuses primarily on the effect of fuel properties on the engine
operating characteristics (injection, fuel spray development, and
combustion), and emissions developed during acceleration.
13
16
13.5
b.m.e.p.=10.52 bar
13
12.5
Bio-fuel
ETH
BUT
BC
VC
12
11.5
Unburned HC (ppm)
Unburned HC (ppm)
14
13
12
b.m.e.p.=7.04 bar
11
Speed
1200 rpm
Unburned HC (ppm)
14
b.m.e.p.=7.04 bar
13
12
11
10
10
15
16
14
b.m.e.p.=3.56 bar
13
12
11
Unburned HC (ppm)
Unburned HC (ppm)
b.m.e.p.=10.52 bar
14
12
13
Unburned HC (ppm)
15
Bio-fuel
ETH
BUT
BC
VC
Speed
1500 rpm
15
b.m.e.p.=3.56 bar
14
13
12
1
2
3
4
Fig. 11. Emitted total unburned hydrocarbons as a function of fuel-bound oxygen in

the fuel blend, for the neat diesel fuel and its various blends with cottonseed oil
(VC), its bio-diesel (BC), ethanol (ETH), and n-butanol (BUT), for the three loads
(b.m.e.p.) at 1200 rpm.
However, for that purpose, the analysis of the phenomena experienced during transient (acceleration) diesel engine operation (e.g.,
turbocharger lag) affecting decisively performance and emissions,
irrespective of the fuel used, is a prerequisite. This has been
detailed recently in a previous publication by the present group
for the engine in hand operated with neat diesel fuel [55], under
various transient operation forms, and it will rst be outlined
(for brevity of space) in the next subsection.
7.1. Outline of basic phenomena during diesel engine acceleration
It has long been established that turbocharger lag is the most
notable off-design feature of diesel engine transient operation,
which signicantly differentiates the torque pattern from the
respective steady-state conditions. Its occurrence is due to the fact
that although the fuel pump responds rapidly to the increased fueling demand after a speed (or load) increase, the turbocharger compressor air-supply cannot match this higher fuel ow instantly, but
only after a number of engine cycles owing to the mechanical, ow
and thermal inertia of the whole system, as no mechanical connection between engine crankshaft and turbocharger shaft exists. This
phenomenon is enhanced by the unfavorable turbocharger compressor characteristics at low engine speeds and loads (boost pressure depending strongly on turbocharger speed). As a result of this
slow reaction, the relative airfuel ratio during the early cycles of
the acceleration assumes very low values (even lower than stoichiometric), thus deteriorating combustion and leading to slow
engine torque and speed response, and hence long recovery period
[1].
An example of this behavior is provided in Fig. 14, where the
lower sub-diagram shows the fuel pump rack response and boost
1
2
3
4
Fig. 12. Emitted total unburned hydrocarbons as a function of fuel-bound oxygen in

the fuel blend, for the neat diesel fuel and its various blends with cottonseed oil
(VC), its bio-diesel (BC), ethanol (ETH), and n-butanol (BUT), for the three loads
(b.m.e.p.) at 1500 rpm.
pressure development during a typical acceleration event with

the engine running on neat diesel fuel. These qualitative remarks
concerning engine and turbocharger response also hold true for
the other fuels examined here. Fuel pump rack reaches its maximum position in four engine cycles, while at the same time interval
(the well known turbocharger lag period) boost pressure remains
practically unchanged, needing almost thirty engine cycles to reach
its maximum value.
This mismatch between fueling and air-supply has a direct
impact on pollutant emissions development, as revealed in the
upper sub-diagram of Fig. 14. As a matter of fact, both nitric oxide
(NO) concentration and smoke opacity obtain peak values during
the turbocharger lag period, which are much higher compared
with their nal steady-state ones (for the case of opacity this is
an order of magnitude higher). Rapid increases in fuel injection
pressure upon the onset of a transient (instantaneous) event cause
the penetration of liquid fuel jet to increase. The higher-momentum fuel jet is not accompanied by equally enhanced gas motion,
resulting in increased liquid fuel impingement on the cool combustion chamber walls, lower mixture preparation rate, and greater
heterogeneity of the mixture [55]. Additionally, the subsequent
harder combustion course prolongs combustion and reduces the
available time for soot oxidation. On the other hand, local high
temperatures that are due to close to stoichiometric airfuel mixtures, formed because of the still low air-supply, are expected to
increase NO formation during the turbocharger lag cycles.
The above qualitative analysis concerns the most notable offdesign feature of diesel engine transient operation, i.e. turbocharger
lag. It applies in all cases detailed in the following subsection, and
this is why it will not be discussed again there. It is to be
14
and so emissions development during the transient event. This is

why the previous example was given for a typical case of engine
acceleration without any quantitative remarks.
14
Speed
1200 rpm
12
0
0
1.09
2.16
b.m.e.p.=10.52 bar
10
Bio-fuel
1.7
3.4
ETH
BUT
BC
VC
1.67
3.34
0
0
0
1.06
b.m.e.p.=7.04 bar
1.7
3.4
2.11
1.67
6
0
3.4
1.67
3.34
1.09
2.16
3.34
0
1.7
7.2. Results of engine accelerations fueled with bio-fuels blends
1.06
2.11
1.06
2.11
1.09
2.16
b.m.e.p.=3.56 bar
2
500
600
700
800
900
1000
1100
1200
Fuel Pump
Rack Position (mm)
Boost Pressure (bar)
NO (ppm)
Opacity (%)
Fig. 13. Emitted Smoke (opacity) nitrogen oxides trade-off, for the neat diesel fuel
and its various blends with cottonseed oil (VC), its bio-diesel (BC), ethanol (ETH),
and n-butanol (BUT), for the three loads (b.m.e.p.) at 1200 rpm. (The small numbers
near the symbols denote values of fuel-bound oxygen in the fuel blend).
10
20
30
40
50
Engine Cycle
Fig. 14. Qualitative fuel pump rack and boost pressure response (lower subgure),
and NO concentration and smoke opacity development (upper subgure) during a
typical acceleration case.
understood, however, that the characteristics of each individual

test (e.g. drivers behavior in automotive use) differentiate the
quantitative results concerning engine and turbocharger response,
In this subsection, for the sake of brevity, the results of Test No.
1 (see Table 5) will only be shown in detail in Fig. 15, while the
results for the other tests were of similar quality but with quantitative differences [50]. This is an eight-folded gure, comprising
the response (with respect to time or equivalently cycle number)
of six engine and turbocharger operating parameters (lower 6
sub-diagrams), as well as of the development of the two exhaust
pollutant emissions, i.e. nitric oxide (NO) in ppm and smoke opacity (% HSU). It is reminded that all of these tests were conducted
with the engine running on neat diesel fuel, constituting the baseline, to which the corresponding cases were compared when using
the blends of diesel fuel with bio-diesel or n-butanol, mentioned at
the end of Section 3.
It is noted that the oxygen mass percentage parameter shown is
found by computation from the in-cylinder trapped air mass and
the fuel pump rack position in conjunction with the pump characteristics (functions of speed and load) [50]. This oxygen mass
includes both the one in the air and the bound one in the fuel,
and it is normalized with respect to the in-cylinder trapped air
mass. This is why a level value of 23.3% (the oxygen content of pure
air by weight) is shown when neat diesel fuel is used. It is stressed
that the extra oxygen in the fuel is very small with respect to its
value in the air, but it is very important for the combustion process
and so the emissions formation, as it actually exists in crucial
places and time instants mainly where a deciency of oxygen prevails. This is the characteristic feature of the diesel engine nature of
heterogeneous mixture formation and combustion.
For all three fuels examined, i.e. the neat diesel fuel and its
blends with either bio-diesel or n-butanol, the fuel pump rack
responds almost instantly to the fueling increase command and
shifts to its maximum position in three engine cycles. Then, it gradually moves backwards to reach its nal steady-state position,
which is practically the same for all tested fuels. The (almost) identical fuel pump rack movement provokes the same acceleration
rates for the three fuels. The same ndings hold true for the turbocharger speed and boost pressure developments. It must be
noted here that slight deviations are unavoidable in a non-electronically controlled test bed. Nevertheless, the deviations observed
here are very modest and not expected to affect the results and
especially the general trends of each fuel blend examined.
On the contrary, as far as pollutant emissions are concerned
(smoke and NO), signicant differences are observed for the three
fuels studied. Specically, smoke opacity presents high deviations.
Both bio-fuels blends decrease smoke emissions of the engine during the transient event compared to the corresponding neat diesel
fuel case, with a follow on improvement observed at the nal
steady-state condition. Also, the improvement in smoke emission
reduction is better for the n-butanol blend than the bio-diesel
blend. This also holds true for their cumulative values and in the
same order, as will be discussed in the next subsection.
Although fuel injection and spray development differ slightly
from the case of neat diesel fuel [62], it is believed that this behavior is due to the engine running effectively overall leaner with
respect to the neat diesel fuel case, since the cylinder trapped relative airfuel ratio remains essentially the same but with the combustion being now assisted by the presence of the fuel-bound
oxygen of the bio-diesel or n-butanol in locally crucial rich zones,
which seems to have the dominant inuence, as it was also discussed for the steady-state cases in the previous section. This is
further supported by the oxygen mass percentage curves of the
15
Test No. 1
Initial conditions: 1016 rpm - 10%
Final conditions: 1880 rpm - 15%
100% Diesel
70% Diesel - 30% Biodiesel
75% Diesel - 25% Butanol
1200
60
800
30
600
110
23.5
Maximum Cylinder
Pressure (bar)
100
23.4
90
80
23.3
Fuel Pump
Rack Position (mm)
70
60
23.2
13
1.20
12
1.15
11
1.10
10
1.05
9
8
Boost Pressure (bar)
200
Oxygen Mass Percentage (%)
15
400
1.00
50,000
2000
Engine Speed (rpm)
Opacity (%)
45
45,000
1800
40,000
1600
35,000
1400
30,000
1200
25,000
1000
Turbocharger Speed (rpm)
NO (ppm)
1000
20,000
0
30
60
90
120
150
180 0
Engine Cycle
30
60
90
120
150
180
Engine Cycle
Fig. 15. Development of engine and turbocharger parameters and emissions response during the acceleration Test No. 1.
relevant subgure of Fig. 15, which reveals the always higher oxygen mass percentage of the n-butanol blend relative to the bio-diesel one that results to its superior behavior.
On the other hand, NO emissions increase for the two bio-fuels
blends compared to the corresponding neat diesel fuel case. These
differences continue at the nal steady-state condition. Moreover,
the NO increase is higher for the bio-diesel blend than the

n-butanol blend. This also holds true for their cumulative values
and in the same order, as will be discussed in the next subsection.
Again, assuming negligible the fuel injection and spray development very slight differentiations, it is believed that this behavior
is predominantly attributed to the strong dependence of NO
16
formation on cylinder gas temperature, which is the one main

parameter apart from the local oxygen availability affecting the
very complex NO formation mechanism. This is conrmed for all
three fuels tested, by calculating the maximum values of the
(mixed mean) cylinder gas temperature. These temperatures were
calculated by applying the ideal gas state equation at the crank
angle where the maximum cylinder pressure appears, noting the
approximation made as actually occurring a little later than maximum cylinder pressure event [50]. It is revealed that these temperatures are higher for the bio-diesel blend, then for the n-butanol
blend, and last for the neat diesel fuel. In that order also proceeds
the increase of emitted NO.
In any case, the leanness and the temperature of the mixture on
a local basis form a delicate balance on NO formation weighting
more or less on the one or the other side, depending on the type
of blends and the specic engine calibration and its operating conditions. The higher maximum temperatures with the bio-fuels
blends may be due to close to stoichiometric airfuel mixtures,
formed because of the still low air-supply during the turbocharger
lag cycles, despite the inuence of the leanness of the mixture
based on a global basis (mixed mean airfuel ratio) with the use
of the bio-fuels (cf. differences of oxygen mass in the relevant subgure of Fig. 15).
7.3. Comparison of engine steady-state and transient emissions results
An attempt is made here to compare the available main regulated emissions of smoke and NO for the neat diesel fuel, bio-diesel
and n-butanol under transient operation, with the corresponding

steady-state bio-fuels blends. Of course, this is done under the
recognition of the highly different non-fuel factors (see previous
subsections) affecting the transient operating schedules, trying to
de-convolute the inuence of the different properties of the tested
bio-fuels.
For that purpose, Fig. 16a and b shows the percentage change of
soot mass and nitrogen oxides mass, respectively, normalized to
the corresponding neat diesel fuel case values, for its blends with
20% of cottonseed bio-diesel or 16% n-butanol, under steady-state
operation for the three loads and the two speeds tested. Similarly,
Fig. 17a and b shows the percentage change of total (cumulative)
soot mass and its peak value and total (cumulative) nitric oxide
mass and its peak value, respectively, normalized to the corresponding neat diesel fuel case values, for its blends with 30% of cottonseed bio-diesel or 25% n-butanol, under transient operation for
the three acceleration tests.
Before proceeding to the comparison, the following issues
should be noted. The instantaneous NO concentration and smoke
opacity values have been rst converted into mass values [50],
and then a summation was executed until each case equilibrates.
Further, it is seen that NOx values are measured for the steadystate tests and NO values for the transient tests. Nevertheless,
given that differences of NOx and NO values are in any case small
and that normalization to the corresponding values for the neat
diesel fuel case is performed, it is expected that any deviations left
are really minimal. The little higher percentages of the bio-diesel or
(a)
Butanol
1200 rpm
Bio-diesel
1500 rpm
Butanol
1500 rpm
-10
-20
-30
Steady States
-40
20% load
40% load
Bio-diesel
Total
Butanol
Total
Bio-diesel
Peak
Butanol
Peak
-10
-20
-30
-40
-50
-60
Transient States
Test 1
Test 2
Test 3
-70
-80
60% load
-50
16
(b)
Nitric Oxide Percent Change wrt Diesel Fuel
(b)
Nitrogen Oxides Percent Change wrt Diesel Fuel
0
Soot Mass Percent Change wrt Diesel Fuel
Soot Mass Percent Change wrt Diesel Fuel
(a)
Bio-diesel
1200 rpm
Steady States
20% load
12
40% load
60% load
-4
-8
Bio-diesel
1200 rpm
Butanol
1200 rpm
Bio-diesel
1500 rpm
Butanol
1500 rpm
Fig. 16. Percentage changes of soot mass (a), and nitrogen oxides mass (b), with
respect to the corresponding neat diesel fuel case values, for its blends with 20% of
cottonseed bio-diesel or 16% n-butanol, under steady-state operation for the three
loads and the two speeds tested.
60
Transient States
Test 1
Test 2
50
Test 3
40
30
20
10
0
Bio-diesel
Total
Butanol
Total
Bio-diesel
Peak
Butanol
Peak
Fig. 17. Percentage changes of total soot mass and its peak value (a), and total nitric
oxide mass and its peak value (b), with respect to the corresponding neat diesel fuel
case values, for its blends with 30% of cottonseed bio-diesel or 25% n-butanol, under
transient operation for the three acceleration tests.
n-butanol in blends with diesel fuel (i.e. higher fuel-bound oxygen

in the fuel blend) for the transient cases are not expected to change
the qualitative comparison between steady-state and transient
operations.
By comparing Figs. 16a and 17a, it is observed that under the
three steady-state loads and the three transient tests (for peak
and cumulative values) examined, a serious decrease in smoke
emissions exists. Furthermore, the mean values for the three loads
in steady-state, separately for the bio-diesel and the n-butanol
blends, are compared with the corresponding mean ones of the
three transients tests (for peak and cumulative values). Much as
this may be considered bold or little speculative, it is attempted
by bearing in mind that during the transient tests various load
and speed conditions are encountered, and that this quasi-steady
approximation of the transient tests will not change the results on
a comparative basis (qualitatively). In all cases, a slight superiority
of the n-butanol blends is revealed against the bio-diesel ones
under steady-state, which is markedly stronger in the case of the
transient operation (higher fuel-bound oxygen in the blend). This
fact points to the main inuence of the fuel-bound oxygen in the
blends and its correct choice as the main variable for comparison.
By comparing now Figs. 16b and 17b, it is observed that under
the three steady-state loads, an increase in NOx emissions exists
with the bio-diesel blend and a slight decrease with the n-butanol
one. On the contrary, under the three transient tests (for peak and
cumulative values) examined an increase in NOx emissions exists
for both blends. Furthermore, as done before, the mean values
for the three loads in steady-state, separately for the bio-diesel
and the n-butanol blends, are compared with the corresponding
mean ones of the three transients tests (for peak and cumulative
values). It is observed that for the bio-diesel blend the increase of
NOx emissions under transient operation is stronger than the
steady-state one, while for the n-butanol blend the slight decrease
of the NOx emissions under steady-state has been inverted into a
mild increase under transient operation. This fact denotes the
inuence of temperatures, which under steady-state operation
are lower for the bio-diesel and even lower for the n-butanol
blends, whereas under transient operation they are higher for the
n-butanol and even higher for the bio-diesel blends, increasing
almost proportionately the NOx emissions. Of course, this behavior
under transient operation is due to the inuence of the airfuel
ratio, which is lower during the turbocharger lag cycles (cf. discussion in Section 7.1.).
8. General discussion on the impact of bio-fuels properties and

comments
The selection for comparison of the fuel-bound oxygen in the
blends as the main common variable (property), which is a parameter strongly inuencing the combustion behavior via the local
fuelair ratio in the various zones and, consequently, the temperatures and emissions formation, was proved very successful under
both steady-state and transient operations.
A monotonic variation of the main emissions of soot and NOx is
revealed with this property. It is a very convenient and welcome
fact that all bio-fuels/diesel fuel blends performed well without
any change of the engine operating conditions, e.g. by optimization
to some parameter.
The rest of the important properties of the bio-fuels blends such
as mainly bulk modulus (of elasticity), kinematic viscosity, lower
heating value and latent heat of evaporation attain by necessity
different values for the same value of the fuel-bound oxygen in
the blend.
The well known smoke-NOx trade-off is defeated with the ethanol or n-butanol blends, i.e. with increasing proportion of either
17
ethanol or n-butanol (in their blends with diesel fuel) a simultaneous decrease of smoke and NOx is effected (at all loads), with the nbutanol blends performing better. This behavior has certainly its
relative merits, but one should not forget the impact of other
parameters when selecting a bio-fuel such as the rest of emissions,
availability, cost, etc.
The lower cetane number (chemical effect) of the bio-alcohols
causes ignition delays and displacement-delay of the HRR diagram,
while the little higher cetane number of the bio-diesel and the vegetable oil (the actual value, as the measured one by the standard
method underrates it) does not cause any discernible displacement-advance of the HRR diagram.
Nevertheless, it should not be forgotten that there is a subtle
interplay of the evaporated fuelair and temperature in the various
zones (of the spray) concerning the heat released by the combusted
amount of fuel, as inuenced by the injection characteristics, latent
heat of evaporation, LHV, cetane number etc, which specify the nal
combustion temperature and oxygen deciency or surplus.
Especially during transient operation, the inuence of the
restricted airfuel ratio during the turbocharger lag cycles has a
profound inuence in increasing NO emissions with the bio-fuels
blends (via the increase of maximum temperatures), while is of
less importance for the smoke emissions where the inuence of
the fuel-bound oxygen contributes to higher smoke reduction (as
for the steady-state case).
9. Conclusions
The present experimental study evaluates the impact of using
blends of diesel fuel with either 10% and 20% (by vol.) cottonseed
oil, or 10% and 20% of its bio-diesel, or 5% and 10% ethanol, or lastly
8% and 16% n-butanol, on the combustion and emissions of a fully
instrumented, six-cylinder, four-stroke, heavy-duty direct injection (HDDI), Mercedes-Benz bus diesel engine, bearing a wastegate turbocharger with after-cooler, running under steady and
transient operating conditions.
The series of steady-state tests were conducted with the engine
working at three loads and two speeds, with measurements taken
of the exhaust soot and exhaust gas regulated emissions. Fuel
injection and cylinder pressure diagrams were simultaneously
obtained for each test case, and a heat release analysis of the combustion chamber pressure diagrams was used.
For the measurements of the transient engine operation schedules of the three acceleration tests examined, where bio-diesel or
n-butanol blends with diesel fuel were tried, the test bed was complemented with fast response instruments to capture the development of key engine and turbocharger variables, depicted in
analytical diagrams, using ultra-fast response instrumentation for
the instantaneous measurements of the exhaust smoke opacity
and NO.
For the steady-state tests, it is revealed that the following hold
true with the use of these bio-fuels blends against the corresponding neat diesel fuel case:
The fuel injection pressure diagrams for the ethanol or nbutanol diesel fuel blends are slightly displaced-delayed,
whereas for the vegetable oil or its bio-diesel diesel fuel blends
no discernible displacement is observed.
The ignition delay is not discernibly changed for the vegetable
oil or its bio-diesel diesel fuel blends, whereas it is increased
for the ethanol or n-butanol diesel fuel blends.
The vegetable oil or its bio-diesel diesel fuel blends show
slightly lower maximum cylinder pressures, which are reduced
more for the cases of ethanol or n-butanol diesel fuel blends.
The maximum cylinder temperatures follow the same pattern.
18
The heat release analysis results, combined with the widely differing physical and chemical properties, are used to aid the correct
interpretation of the observed engine emissions behavior, on a
comparative basis, when using these bio-fuels blends as follows:
Signicant reduction of smoke opacity with all bio-fuels diesel
fuel blends against the corresponding neat diesel fuel case,
which is a monotonic function of the percentage of bio-fuel in
the blend.
Slight reduction of emitted nitrogen oxides with the ethanol or nbutanol diesel fuel blends and corresponding slight increase with
the vegetable oil or its bio-diesel diesel fuel blends, against the
corresponding neat diesel fuel case, with these variations being
monotonic functions of the percentage of bio-fuel in the blend.
The Smoke NOx trade-off is defeated with the ethanol or
n-butanol blends, i.e. with increasing proportion of either
ethanol or n-butanol (in their blends with diesel fuel) a simultaneous decrease of smoke and NOx is effected, with the
n-butanol blends performing better.
With the exemption of the vegetable oil blends, all the other
bio-fuels diesel fuel blends show a decrease of CO emissions,
whereas all the bio-fuels diesel fuel blends show an increase
of unburned HC emissions.
Concerning smoke and NO exhaust emissions for the three
acceleration tests examined, using neat diesel fuel and its
blends with bio-diesel or n-butanol, apart from the impact of
properties of bio-fuels, the inuence of the restricted airfuel
ratio during the turbocharger lag cycles should be considered.
This has a profound inuence on increasing NO emissions with
the bio-fuels blends (via the increase of maximum temperatures), while it is of less importance for the smoke emissions
where the inuence of the fuel-bound oxygen contributes to
smoke reduction (as for the steady-state case).
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Fuel 156 (2015) 119

Contents lists available at ScienceDirect

Impact of properties of vegetable oil, bio-diesel, ethanol and n-butanol

the domain of engine- [1] or fuel-related techniques [2]. The latter

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

fuel consumption and reduction of pollutant emissions. This has

total unburned hydrocarbons

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

differing bio-fuels properties among themselves and those of the

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

Mercedes-Benz, OM 366 LA, 6-cylinder, in-line,

Shaft encoder (engine

180 270 360

Cylinder exhaust line

in ppm (parts per million, by vol.) in the exhaust was measured

Injector body and nozzle

Static injection timing

concentration (in ppm) in the exhaust was measured with a

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

exhaust gas sample owing continuously through the opacimeter

2.3. Measurement of engine and turbocharger operating parameters

Kistler shaft encoder

Fuel pump rack position

together with their measuring error, while more details can be

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

comparative purposes, in order to explain qualitatively the relative

4. Parameters tested and experimental procedure

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

Properties of the cylinder content are provided as fourth order

6. Presentation and discussion of steady-state results

6.1. Combustion heat release analysis results

Engine Speed (rpm)

fuel blend (described previously) assuring the best possible

In this subsection, results are presented in the four subgures of

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

Fuel pressure (bar)

Cylinder pressure (bar)

Degrees crank angle

VC20-D, 20% load

Degrees crank angle

Gross heat release rate (J/deg.)

Degrees crank angle

VC20-D, 20% load

The behavior of the fuel pressure diagrams is attributed to the

Figs. 3b and 4b show the corresponding cylinder pressure

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

Fuel pressure (bar)

Cylinder pressure (bar)

ET10-D, 20% load

ET10-D, 20% load

D.C. Rakopoulos et al. / Fuel 156 (2015) 119

6.2. Emissions results

Smoke Opacity (% Hartridge)

Fig. 5. Emitted (soot) smoke opacity (% Hartridge) as a function of fuel-bound

Smoke Opacity (% Hartridge)

Fig. 6. Emitted (soot) smoke opacity (% Hartridge) as a function of fuel-bound

blends are bracketed by the former ones. This variable inuences

Nitrogen Oxides (ppm)

Nitrogen Oxides (ppm)

Nitrogen Oxides (ppm)

Nitrogen Oxides (ppm)

Nitrogen Oxides (ppm)

Nitrogen Oxides (ppm)

D.C. Rakopoulos et al. / Fuel 156 (2015) 119