Energy Fuels 2009, 23, 4343–4354 : DOI:10.

1021/ef900448m
Published on Web 07/28/2009

Effect of Ethanol on Blending Stability and Diesel Engine Emissions

Magı́n Lapuerta,* Octavio Armas, and Reyes Garcı́a-Contreras
Escuela T
ecnica Superior de Ingenieros Industriales, University of Castilla;La Mancha, Edificio Polit
ecnico, Avda. Camilo Jos
e
Cela, s/n 13071, Ciudad Real, Spain

Received May 12, 2009. Revised Manuscript Received July 7, 2009

The stability diagrams of ethanol (e)-biodiesel (b)-diesel blends were studied at different temperatures. It was
found that biodiesel acts as a stabilizer component in e-diesel blends, except at low temperatures, where it
favors the formation of a gelatinous phase. Three blends (two e-diesel and an e-b-diesel) were selected to
be tested in a diesel engine, and their performance and emissions were compared to those of a reference diesel
fuel. The results show that, with increasing ethanol content in the blends, hydrocarbon emissions increase
significantly because of the high heat of vaporization of alcohol, thus promoting the appearance of a nuclei
mode. With all of the blends tested, reductions in smoke opacity and particulate matter emissions with
respect to diesel fuel are obtained, but these decreases were not lineal with the oxygen content. The oxygen
provided by ethanol resulted in more efficiency in the opacity reduction than the oxygen provided by methyl
ester (e-b-diesel blend), but in the case of particulate matter emissions, the opposite trend was observed.

1. Introduction experiences, reductions in smoke opacity or particulate matter

(PM) emissions were already reported, this currently being
The recently approved European directive “on the promo-
an additional benefit of their use as a consequence of the in-
tion of the use of energy from renewable sources” 2009/28/CE
creasingly stringent emission regulations (Euro IV and Euro V),
establishes a new objective of 10%, in energy basis, for bio-
which will soon be entry into force. However, the blending
fuel consumption in the transportation sector before 2020.1
proportion of ethanol is limited because of its low ignitability,
Different alternatives must be offered by the biofuel producers
its low lubricity, and its reduced heating value.7,8 Another
to fulfill such a target, with them being compatible with the
limit for blending is imposed by the limited miscibility with
stringent requirements in life-cycle greenhouse emissions,
petroleum diesel. Although at ambient temperature, the
which have also been included in the same directive. In the first
miscibility is quite good, at temperatures below 10 °C, the
period (2010-2017), savings higher than 35% will be required
miscibility is sharply reduced, which often makes the incor-
with respect to the greenhouse emissions typically obtained
poration of a stabilizing additive necessary.9,10 Additionally,
from diesel or gasoline fuels. Ethanol is one of the automotive
the presence of moisture reduces the miscibility. In fact, the
fuels that will provide the highest life-cycle greenhouse emission
ethanol used for blending in Europe must be anhydrous as
savings as soon as second-generation production processes,
specified in the norm EN-15376.
such as cellulosic fermentation from wheat straw, waste wood,
The mentioned blending limitations are significantly re-
or farmed wood, are consolidated. However, to guarantee the
duced as a consequence of the progressive incorporation of
fulfilment of this target, the increasing dieselization process
biodiesel in the commercial diesel fuel, because biodiesel fuels
occurring in Europe must also be considered (i.e., in Spain,
improve the stability of the blends, and compensate for the
diesel fuels constitute more than two-thirds of the automotive
reduction in cetane number and lubricity derived from the
fuel consumption). Ethanol can participate as a renewable
addition of ethanol. Therefore, in this work, a study about
alternative for the consumption of biofuels not only in spark-
the blending stability and the engine emissions with ethanol
ignition engines but also in diesel ones, in two ways: as biodiesel
(e)-biodiesel (b)-diesel blends is presented. This study is an
produced by transesterification with ethanol and as a fuel for
extension to a previous study about ethanol (e)-diesel blends
direct blending with either petroleum diesel, biodiesel, or both
already presented separately in refs 11-13, devoted to blending
of them.
stability, steady-condition engine emissions, and transient-
Ethanol was first used in diesel engines in the 1970s in South
condition engine emissions, respectively. Other authors have
Africa2 and further on in the 1980s in Japan,3 Germany,4
and United States,5 as reviewed in ref 6. In most of these
(7) Satge de Caro, P.; Mouloungui, Z.; Vaitilingom, G.; Berge, J. Ch.
Fuel 2001, 80, 565–574.
(8) Xing-cai, L.; Jiang-guang, Y.; Wu-gao, Z.; Zhen, H. Fuel 2004, 83,
*To whom correspondence should be addressed. Telephone: þ34- 2013–2020.
926295431. Fax: þ34-926295361. E-mail: magin.lapuerta@uclm.es. (9) Hansen, A. C.; Zhang, Q.; Lyne, P. W. L. Bioresour. Technol. 2006,
(1) Directive 28/2009/CE of the European Parliament and the Council 96, 277–285.
on the Promotion of the Use of Energy from Renewable Sources, 2009. (10) Waterland, L. R.; Venkatesh, S.; Unnash, S. Safety and perfor-
(2) Letcher, T. M. S. Afr. J. Sci. 1983, 79, 4–7. mance assessment of ethanol/diesel blends (e-diesel), 2003; NREL/SR-
(3) Murayama, T.; Miyamoto, N.; Chikahisa, T.; Ogawa, H. SAE 540-34817.
Tech. Pap. 830373, 1983. (11) Lapuerta, M.; Armas, O.; Garcı́a-Contreras, R. Fuel 2007, 86,
(4) Weidmann, K.; Menrad, H. SAE Tech. Pap. 841331, 1985. 1351–1357.
(5) Likos, B.; Callahan, T. J.; Moses, C. A. SAE Tech. Pap. 821039, 1983. (12) Lapuerta, M.; Armas, O.; Herreros, J. M. Fuel 2008, 87, 25–31.
(6) Rakopoulos, C. D.; Antonopoulos, K. A.; Rakopoulos, D. C. (13) Armas, O.; Cardenas, M. D.; Mata, C. SAE Tech. Pap. 2007-
Energy 2007, 32, 1791–1808. 24-0131, 2007.

r 2009 American Chemical Society 4343 pubs.acs.org/EF

Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m Lapuerta et al.

Table 1. Fuel Properties

properties diesel soyate biodiesel bioethanol ED7.7 EBD ED17
density at 15 °C (kg/m )
3
834.9 885 792 831 844 827
viscosity at 40 °C (cSt) 2.72 4.09 1.13 2.41 2.63 2.12
gross heating value (MJ/kg) 45.54 39.42 28.05 43.82 42.37 41.93
lower heating value (MJ/kg) 42.58 36.87 25.22 40.86 39.53 38.99
flash point (°C) 58.5 174 12
sulfur (ppm w) 33.9 2.5
water (ppm w) 57 272 2024 243 343 618
CFPP (°C) -19 -3 -19 -14 -18
molecular formula C15.18H29.13 C18.81H34.69O2 C2H6O C11.66H22.96O0.27 C12.12H23.61O0.64 C8.96H18.22O0.47
C (% w/w) 86.13 77.13 52.14 83.63 81.07 80.60
H (% w/w) 13.87 11.94 13.13 13.82 13.26 13.75
O (% w/w) 0 10.93 34.73 2.55 5.67 5.65
molecular weight (g/mol) 211.7 292.9 46.06 167.5 179.53 133.56
stoichiometric fuel/air ratio 1:14.67 1:12.50 1:9 1:14.25 1:13.63 1:13.74

also presented previous studies about the stability of e-b-diesel Table 2. Engine Specifications
blends14,15 and their effect on engine emissions,16-18 but only in fuel injection common rail, with pilot injection
ref 19 e-diesel and e-b-diesel blends were compared. Finally, maximum power 82 kW at 4000 rpm
maximum torque 248 N m at 2000 rpm
an analysis about the effect of the oxygen content on the gaseous cylinder arrangement 4 cylinders, in line
emissions, smoke opacity, and PM emissions is presented, trying bore 86.5 mm
to discern if the observed reductions can be correlated with the stroke 94 mm
oxygen content of the fuel or if they depend upon the functional displacement 2.2 L
compression ratio 18:1
group containing oxygen.

2. Fuels The composition and most important properties of pure

The stability of e-diesel and e-b-diesel blends mainly
depends upon temperature, humidity, and fuel composition.
A previous study concluded that, with the use of hydrated
ethanol, the miscibility of ethanol in diesel decreases.11 In this
work, anhydrous ethanol (99.7%) provided by Abengoa Bio-
energy has been used. Reference fuel is a typical low-sulfur
diesel fuel similar to those available in Spanish petrol stations
supplied by Repsol. The biodiesel selected to make stability
studies and prepare the e-b-diesel blend for engine testing was
soybean methyl ester, also provided by Repsol. The selection of
soyate biodiesel is justified because this fuel presents typical
properties of biodiesel fuels and has been previously used in
other studies with e-b-d diesel blends.17,18,20
From the stability study, three blends have been selected to
carry out the engine tests: (1) e-diesel blend (ED7.7), com-
posed of 7.7% ethanol, 0.62% additive O2Diesel (acting as a
stabilizer and as a cetane improver), and 91.68% diesel, with
all percentages in volume. This ethanol content ensures the
stability of the blend in a wide temperature range. This blend is
denoted as ED7.7. (2) e-b-diesel blend (EBD), composed of
7.7% ethanol and a blend of 30% of soybean biodiesel-diesel.
This biodiesel content has received major commercial interest
up to now in both delivery models: captive fleets and petrol
stations. (3) e-diesel blend (ED17), composed of 17% ethanol,
with this percentage being close to the limit of e-diesel blends
stability at ambient temperature. This ethanol content has been
selected because this blend has the same oxygen content as
EBD fuel, while belonging to a different functional group.
(14) Fernando, S. Energy Fuels 2004, 18, 1695–1703.
(15) Makareviciene, V.; Sendzikiene, E.; Janulis, P. Bioresour. Tech-
nol. 2005, 96, 611–616.
(16) Chen, H.; Shuai, S.-J.; Wang, J.-X. Proc. Combust. Inst. 2006, 31,
2981–2989.
(17) Shi, X.; Yu, Y.; He, H.; Shuai, S.; Wang, J.; Li, R. Fuel 2005, 84,
1543–1549.
(18) Xiaoyan, S.; Xiaobing, P.; Yujing, M. Atmos. Environ. 2006, 40,
2567–2574.
(19) Kwanchareon, P.; Luengnaruemitchai, A.; Jai-In, S. Fuel 2007,
86, 1053–1061.
(20) Fernando, S.; Hanna, M. Trans. ASAE 2005, 48 (3), 903–908.
4344
fuels and tested blends with regard to the engine operation are
shown in Table 1. Although the diesel composition has been
provided by Repsol, all other properties shown have been
measured in our laboratory.
3. Experimental Equipment and Test Conditions
The stability and rate of separation of e-b-diesel blends were
obtained by means of optical equipment (Turbiscan), specifically
designed for the characterization of liquid emulsion suspensions
and solutions. The device has an infrared light source of 850 nm
wavelength and two detectors operating simultaneously. The first
one detects the light transmitted with no refraction and is located
in the prolongation of the light beam (0°), while the second one
detects the backscattered light in the direction 135° with respect to
the incident light beam. Other characteristics of Turbiscan are
described in ref 11.
Different tests were carried out to study the influence of
ethanol and biodiesel content on the stability of blends at
different temperatures. As the temperature decreases, the region
of unstable blends becomes larger and, therefore, a higher
number of blends must be tested to determine the boundary
between the stable/unstable region and the limit between the
different unstable subregions.
To determine the composition of the separated phase in
unstable blends (Section 6), a Shimadzu GC-14 gas chromato-
graph has been used. The detector was a flame ionization detector
(FID) with helium as a carrier gas and a capillary column
Supelwax adequate for alcohol detection. The column oven
temperature started at 40 °C was held for 4 min and increased
at 250 °C at a rate of 25 °C/min.
Engine tests were carried out in a 4-cylinder, 4-stroke, turbo-
charged, intercooled, common-rail, 2.2 L Nissan diesel engine
(which can be considered typical of those used in European diesel
vehicles) joined to an asynchronous electric brake Schenck Dynas
III LI 250. The main specifications of the engine are given in
Table 2, and the experimental layout is shown in Figure 1.
The brake control system allowed for the measurement and
control of the engine speed, throttle position, and torque. Because
emissions are strongly dependent upon the exhaust gas recircula-
tion (EGR) ratio, it is important to keep this parameter fixed
when comparing different fuels. For this reason, the EGR valve
was driven by a stepper motor, which allows for acheiving the
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 1. Experimental installation.
Table 3. Set Values of Tested Engine Modes
speed (rpm) effective torque (N m)
mode value RSD (%) value RSD (%)
U10 2126 0.017 8 8.807
C0 1410 0.016 26
F 1526 0.007 46
G0 1743 0.017 77
H 1853 0.026 110
same EGR ratio for all tested fuels. Herein, the EGR ratio was
defined as the mass flow of the recirculating exhaust normalized
by the total mass flow entering the cylinder. Fuel consumption
was measured with a gravimetric fuel balance AVL 733-S
(measurement errors below 0.12%), and air consumption was
measured with a hot-wire sensor Siemens 5WK9628. The engine
was also equipped with the necessary instrumentation for the
measurement and monitoring of operating temperatures and
pressures (intake air, fuel, exhaust gases, lube oil, etc.).
PM was collected using a partial flow mini-tunnel (Nova
Microtrol) equipped with mass flow controllers to achieve the set
value of the dilution ratio. A portion of the exhaust gas was
sampled in the center of the exhaust pipe to avoid capturing wall
deposits. This portion of gas was routed into the mini-tunnel,
where it was mixed with filtered ambient air. This diluted flow was
then driven across a Whatman glass microfiber 70 mm filter, which
was weighed before and after sampling using a Sartorius M5P
analytical balance to determine the total mass of PM collected on
the filter. The filters were conditioned before every weighing in a
climatic chamber (Minitest CCM-0/81), to obtain the same tem-
perature and humidity conditions. The collection and conditioning
procedure was optimized as described in ref 21. Finally, the filters
were subjected to a thermal extraction method (providing the
volatile organic fraction of the PM, VOF) by means of a thermo-
gravimetric analyzer, with this method being described in ref 22.
Particle size distributions were determined using the partial
dilution mini-tunnel and a scanning mobility particle sizer
(SMPS) TSI 3936L10. This method was previously optimized
in ref 23. Particles were sampled from the dilution mini-tunnel,
and the large ones were removed by a 610 nm impactor. These
particles are transported to a differential mobility analyzer
(21) Lapuerta, M.; Armas, O.; Ballesteros, R.; Duran, A. SAE Tech.
Pap. 99-01-3531, 1999.
(22) Lapuerta, M.; Ballesteros, R.; Rodrı́guez-Fernandez, J. Measure-
ment Science and Technology 2007, 18, 650–658.
(23) Armas, O.; Gomez, A.; Herreros, J. M. Meas. Sci. Technol. 2007,
18, 2121–2130.
Lapuerta et al.
bmep (bar) EGR ratio (%)
value RSD (%) value RSD (%)
0.46 8.807 25 5.766
3.987 1.50 3.987 14 6.469
0.684 2.65 0.684 10 8.028
0.811 4.44 0.811 0 0
1.007 6.34 1.007 0 0
(DMA), where a voltage is applied and particles are classified
according to their electrostatic mobility ratio. Finally, they are
counted in a condensation particle counter (CPC). A correction
for particles with multiple charges was automatically applied by
the control software. The total concentration and the mean
diameter of the distribution were calculated by integrating over
the particle diameter variation range of the distributions. The
concentration was appropriately scaled to express it as in the raw
exhaust, because particles were sampled from the dilution mini-
tunnel and not from the exhaust pipe.
Nitrogen oxide (NOx) emissions were recorded with a chemio-
luminiscence analyzer Topaze 3020, and total hydrocarbon emis-
sions (THC) were measured with a flame ionization detector
Graphite 52M-D (errors below 0.5%), both integrated in a
sampling and conditioning system Environnement. A smoke-
meter AVL 439 was used to measure the smoke opacity (in
percentages of the light absorbed or dispersed with respect to
the intensity of the emitted beam, with less than 0.1% errors).
Five operating modes were selected among the collection of
steady stages which reproduce the transient cycle that vehicles
with this type of engine must follow for certification according to
the European Emission Directive 70/220, amendment 2001/C 240
E/01. The selection of modes C0 , F, G0 , and H was made based on
the highest contribution to the total PM emissions,25 while mode
U10 was chosen because it was the mode with the highest total
hydrocarbon (THC) emissions. Table 3 shows the set values
established for engine speed, effective torque, brake mean effec-
tive pressure (bmep), and EGR ratio at each operation mode,
together with the relative standard deviation (RSD) of the values
attained during the tests. It can be observed that the repeatability
was lower in mode U10 than in the other modes, as a consequence
of the typically low engine stability at such a low load.
(24) Lapuerta, M.; Armas, O.; Hernandez, J. J. Appl. Therm. Eng.
1999, 19, 513–529.
(25) Lapuerta, M.; Armas, O.; Ballesteros, R.; Fernandez, J. Fuel
2005, 84, 773–780.
4345
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
After each change of fuel, all lines were drained and then filled
with the next fuel. Before beginning a new test, the sample lines
were cleaned to remove deposits and hydrocarbons of the pre-
vious tests. After that, the engine was warmed with the new fuel
for at least 1 h to purge any remains of the previously tested fuel
from the engine fuel system. Additionally, the reference fuel
(REF) was tested prior to every biodiesel blend. The duration
of each operation mode was chosen, so that three different
particulate filters could accumulate a particulate mass of at least
1.3 mg for each one and six particle size distributions could be
taken with the SMPS.
4. Interpretation of Stability Profiles
The transmission profiles provided by Turbiscan (instru-
ment described in Section 3) must be interpreted to obtain the
stability results. e-diesel or e-b-diesel blends are considered
stable when components that constitute these blends are mixed
completely, leading to a single homogeneous, clear, and trans-
parent phase. In this case, the obtained Turbiscan profiles along
the test time are superposed. On the contrary, when separation
of phases occurs (unstable blend), the profiles do not superpose
each other with time.11
The phase separation process could generate different types
of unstable blends, such as two liquid phases, a gelatinous
interphase, or the formation of a gelatinous phase in the
bottom of the glass cell. Each one of these unstable patterns
is described in the following paragraphs:
(A) Two liquid phases. At positive temperatures and when
blends contain between 15 and 75% of ethanol, two
different liquids phases are distinguished after the
separation. The separation process begins when the
sample turns quickly into a turbid phase, with no
distinction between the two phases. Later, a more
transparent phase in the upper part of the mixture is
distinguished, corresponding to ethanol, although the
phase below the interphase maintains the turbidity.
Finally, the width of the bioethanol phase increases,
moving the interphase toward a lower position until
equilibrium is reached, whereas the phase located
below becomes transparent.
(B) Gel formation in the interphase. At temperatures
below 0 °C and when blends contain between 10 and
60% ethanol, a gelatinous phase is generated and
located in the interphase between the two liquid
phases. The main difference between a liquid and
gel interphase is its thickness, with the latter being
thicker (>1 mm). From its very early formation, the
appearance of this interphase is already gelatinous.
The stages of this phase separation process are
similar to that described in A.
(C) Gel formation in the inferior part of the glass cell.
When the ethanol content is high and tests are
carried out at low temperature, a gelatinous phase
appears in the inferior part of the cell glass. First, it
was thought that biodiesel prompted this gel forma-
tion because this temperature is similar to the cold-
filter plugging point (CFPP) value of methyl ester.
However, the gelatinous phase is generated in e-
diesel blends too. Although the e-diesel interaction
is the main cause for this gel formation, the biodiesel
presence favors this phase. After an initial turbidity is
observed in these unstable blends, small crystals
appear along the glass cell, which are suspended in
the liquid phase during the separation process. These
4346
Lapuerta et al.
crystals are mixed in the bottom of the cell, present-
ing a gelatinous aspect, whereas a liquid phase is
distinguished in the upper part of the cell glass. The
phase laying above the gelatinous one is not always a
homogeneous liquid phase. There are some condi-
tions under which two liquid phases appear separa-
ted by an interphase.
5. Parameters of Stability
From the transmission profiles of unstable blends, some
information about the composition of the phases can be
obtained. A non-dimensional parameter, which is defined as
the separation ratio (SR), indicates the final/maximum
volume of separated ethanol (when the phase separation
process has finished, Vsep) with respect to the initial ethanol
content in the blend (Ve)
Vsep hsep
SR ¼ ¼ ð1Þ
Ve he
Because the section along the glass cell is constant, the
separation ratio can be expressed as a ratio of heights (eq 1),
where hsep is the final/maximum height of the separated phase
and he is the height of the initial content of ethanol. These
values can be obtained from the Turbiscan software.
The SR increases as the ethanol content becomes higher in
both e-diesel and e-b-diesel blends. In some conditions,
values of SR higher than unity are obtained. This result would
indicate that the separated phase is composed of more ethanol
than the initial volume in the blend, which is not possible. In
fact, in the migration process of ethanol toward the superior
part of the cell, either diesel or biodiesel is dragged, indicating
that the separated phase is not only composed of ethanol.
Therefore, another non-dimensional parameter has been
defined, dragging ratio (DR), indicating the content of diesel,
biodiesel, or both that is present in the separated phase. This
parameter is defined as the ratio between the height of the
separated phase (diesel and biodiesel, hd,sep and hb,sep) and that
corresponding to the initial diesel-biodiesel blend. To calcu-
late this parameter, all of the blended ethanol is considered to
belong to the separated phase.
hsep - he hd, sep þ hb, sep
DR ¼ ¼ ð2Þ
hblend - he hd þ hb
6. Composition of the Separated Phase
The composition of the separated phase of an unstable
e-b-diesel blend (only in the case of two liquid phases) was
analyzed using a Shimadzu GC-14 chromatograph (described
in Section 3). A previous study concluded that the separated
phase from the e-diesel blend with 20% ethanol was majority
composed of ethanol,11 with this conclusion allowing for the
use of the parameter SR.
Chromatographic analysis of pure components that form
e-b-diesel blends (ethanol, biodiesel, and diesel) have been
carried out, and they are shown in Figure 2. While in the figure
of ethanol analysis a single peak is shown for low retention
time, in the diesel profile, many peaks appear because it is
composed by many different hydrocarbons. The detection of
biodiesel fuel occurs from the 20th minute, indicating that it is
the heaviest component of the three tested fuels.
Figure 3 shows the chromatography analysis of the sepa-
rated phase of the E45B5 blend at 0 °C, which presents a SR
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 2. Chromatographic analysis of pure components.
Figure 3. Chromatographic analysis of the separated phase of the
E45B5 blend at 0 °C.
value higher than 1 (dragging ratio zone). In this figure, a
large peak appears in the first moments, indicating the pre-
sence of ethanol. From minutes 10 to 20, several peaks
are shown corresponding to diesel fuel, and in last minutes,
some peaks corresponding to biodiesel fuel are observed.
Therefore, when ethanol content in the blend is higher than
25% (blends situated in the DR zone), the alcohol, in its
migration process, drags diesel and biodiesel toward the upper
phase, as described above. This result justifies the use of the
DR instead of the SR. Another analysis made from a sample
taken from the lower phase of this blend (although not
presented here) showed a very minor ethanol content, justify-
ing the definition given in eq 2.
7. Effect of the Composition and Temperature on Stability
The effect of ethanol and biodiesel content at different
temperatures has been studied. Ternary diagrams are used
to show the stability results of e-b-diesel blends. This kind of
4347
Lapuerta et al.
diagram is widely used in the study of ternary blends15,19,20
because it allows us to study simultaneously the influence of
the three components of the blends at a single temperature. At
each temperature tested, the limit of the stability region is
depicted. The shape of the unstable zone is similar to that
obtained by other authors.15
The limit between the stable and unstable regions corres-
ponding to 10 °C is shown in Figure 4a. This was chosen as the
first temperature to be tested because most of the literature
reports engine problems derived from unstability below this
temperature, with these problems becoming even greater at
lower temperatures.9,10 Two zones can be distinguished in
the unstable region corresponding to two different types of
unstable blends: blends that present a certain separation
ratio and blends defined by their dragging ratio. Iso-lines
indicate different values of SR or DR at the final equilibrium
state.
In the SR zone, it can be observed that, the higher the
ethanol content, the higher the separated phase, while bio-
diesel generates the opposite effect (it improves the stability of
the blends) because it acts as a stabilizer. In the DR region,
the separated phase is not only composed of ethanol (see
Section 6). Ethanol presents a good miscibility with biodiesel
because of its polar character,19 but there are e-diesel blends
(containing no biodiesel) that also present DR, indicating that
biodiesel is not the only component that can be dragged by
ethanol. Biodiesel improves stability, but in the DR region,
the higher the biodiesel content in the blends, the higher the
DR values.
Figure 4b shows the stable region obtained at 5 °C, which is
smaller than the zone corresponding to 10 °C. Again, the
increase of ethanol content promotes the phase separation,
while biodiesel stabilizes the blends. Although this is a positive
temperature and it is far from the CFPP values of fuels, a
gelatinous phase appears in the bottom of the cell glass when
the ethanol content is very high (75%) and the content of
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 4. Stability results at different temperatures.
biodiesel is small (less than 10%). Above this gelatinous layer,
a homogeneous and clear phase is formed. The region corre-
sponding to these blends is defined as G-1L.
The gel formation could be caused by the presence of
biodiesel because this is the component with the highest CFPP
value. However, in e-diesel blends this phase appears too.
4348
Lapuerta et al.
Therefore, it must be concluded that, although the gel forma-
tion is derived from the combination of e-diesel, the presence
of biodiesel highly influences the formation of this gel. Etha-
nol has a very low freezing point. Therefore, it could be ex-
pected that e-diesel and e-b-diesel improve cold-flow prop-
erties with respect to diesel and biodiesel fuels. However, while
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m Lapuerta et al.

Figure 5. Brake-specific fuel consumption and thermal efficiency.

Figure 6. Absolute and relative fuel/air ratio.

the pour point of e-diesel blends decreases significantly with 8. Engine Emissions
respect to that of diesel fuel, the cloud point increases.26
8.1. Engine Operating Conditions and Performance. At
At 0 °C (Figure 4c), the influence of ethanol and biodiesel
each operation mode, the EGR ratio, effective torque, and
content is similar to that at the previous studied temperatures,
engine speed were established, as listed in Table 3, regardless
but the region in which the gelatinous phase (G-1L) appears
of fuel consumption. All of the variables are plotted in
becomes larger as the biodiesel content becomes higher (until
Figures 5-11 against the bmep, with the latter being derived
30%). At this temperature, a new region appears located
from the effective torque. Mode U10 is plotted separately
between DR and G-1L, where unstable blends present a
from the rest of the modes, because no increasing bmep
gelatinous phase in the bottom of glass cell and two liquid
accompanies the increased engine speed in this case. Small
phases appear in the upper part (G-2L).
variations are obtained in the values of the EGR ratio with
Two negative temperature values have been chosen (-2 and
different fuels (Table 3), especially at low load. To obtain the
-5 °C) above and below the biodiesel CFPP value. At -2 °C
same torque and power output for every tested fuel, the
(Figure 4d), an important increase of the unstable region is
break-specific fuel consumption (bsfc) was higher for etha-
observed with respect to that obtained at 0 °C. This could be
nol blends because these fuels present a lower heating value
explained by the enlargement of the G-1L region with respect to
than diesel (left panel of Figure 5), but ED7.7 shows similar
positive temperatures. While biodiesel benefits stability when
values to diesel. The brake thermal efficiency (right panel of
ethanol content is low, it increases the gel formation at high
Figure 5) of different fuels is similar in low-load conditions,
ethanol percentages. Above this temperature, all biodiesel-
although in mode H, e-diesel blends (especially ED7.7)
diesel and ethanol-biodiesel blends remain stable, but at this
present slightly higher values, with this trend being in agree-
value, there are some ethanol-biodiesel blends in which the
ment with that observed by other authors.27,28
gelatinous phase appears. Most of the blends situated in the
The measured differences in absolute fuel/air ratios of
SR or DR zone at positive temperatures show a gelatinous
ethanol blends with respect to diesel (left panel of Figure 6)
interphase (new phase, GI) between two liquid phases.
were compensated by the different combustion stoichiometric
The lowest temperature tested was -5 °C, being below the CFPP
values, leading to similar relative fuel/air ratios (right panel of
value of biodiesel. In this case, only pure ethanol, pure diesel, and
Figure 6), except the ED7.7 blend that presents relative fuel/air
the e-diesel blends up to 5% of alcohol remain stable (Figure 4e),
ratios lower than other fuels at high load because of its lower
indicating that, at this temperature, biodiesel promotes gel forma-
tion (biodiesel does not act as a stabilizer any more).
(27) Li, D.-G.; Zhen, H.; Xingcai, L.; Wu-gao, Z.; Jian-guang, Y.
Renewable Energy 2005, 30, 967–976.
(26) McCormick, R. L.; Parish, R. Advanced petroleum based fuels (28) Abu-Qudais, M.; Haddad, O.; Qudaisat, M. Energy Convers.
program and renewable diesel program, 2001; NREL/MP-540-32674. Manage. 2000, 41, 389–399.
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Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 7. THC and NOx emissions.
Figure 8. Smoke opacity and PM emissions.
Figure 9. Volatile organic fraction of the PM.
bsfc. The relative fuel/air ratio is a parameter with an important
influence in emissions; therefore, the similar values obtained
with different fuels tested indicate that the differences in
emissions could be attributed to the composition and properties
of these fuels and not the relative fuel/air ratio.
8.2. Gaseous Emissions. Total hydrocarbon emissions for
different fuels are shown in the left panel of Figure 7. While
blends with 7.7% of ethanol present THC emissions similar
to diesel, the gaseous emissions from the blend with the
highest ethanol content are higher, especially in mode U10.
In low-load conditions, the atomization, evaporation, and
(29) Sayin, C.; Uslu, K.; Canakci, M. Renewable Energy 2008, 33,
1314–1323.
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Lapuerta et al.
fuel distribution processes are less favorable.29 The higher
heat of vaporization of ethanol favors an increment in the
hydrocarbon emission with respect than that with diesel. The
results obtained in this work are in agreement with that
observed by other authors.6,27,30 Therefore, little ethanol
content and biodiesel presence have no influence on THC
emissions, but a higher alcohol content in the blends affects
these gaseous emissions.
NOx emissions of fuels tested are shown in the right panel of
Figure 7. It is observed that emissions from ethanol blends are
slightly lower than those from reference fuel in C0 , F, and G0
modes. No difference can be observed between ED17 and EBD,
thus showing that neither further ethanol content nor the addition
of biodiesel provides further reductions in NOx emissions.
8.3. Smoke Opacity and PM. Smoke opacity is indicative of
dry soot emissions, which are one of the main components of
PM.16,31 The smoke opacity decreases as the ethanol content in
the blend becomes higher (right panel of Figure 8), in agree-
ment with all of the literature reviewed.6,8,16,31-33 This reduc-
tion is more important at high-load modes.34,35 The lower
opacity can be explained because the presence of fuel oxygen
(30) Kass, M. D.; Thomas, J. F.; Storey, J. M.; Domingo, N.; Wade,
J.; Kenreck, G. SAE Tech. Pap. 2001-01-2018, 2001.
(31) Chen, H.; Wang, J.; Shuai, S.; Chen, W. Fuel 2008, 87, 3462–
3468.
(32) Shih, L. K. SAE Tech. Pap. 982573, 1998.
(33) He, B. Q.; Shuai, S. J.; Wang, J. X.; He, H. Atmos. Environ. 2003,
37, 4965–4971.
(34) Di, Y.; Cheung, C. S.; Huang, Z. J. Aerosol Sci. 2009, 40, 101–
112.
(35) Choi, C. Y.; Reitz, R. D. Fuel 1999, 78, 1313–1317.
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 10. Particle size distributions for C0 and H engine modes.
Figure 11. Mean diameter (dm) and total particle number concentration (PNC).
reduces the probability of rich-zone formation (high local fuel/
air ratio) and promotes the oxidation of soot nuclei generated
in fuel combustion. Among the two fuels with the same ethanol
content, the smoke opacity of EBD is lower, corresponding to
the additional biodiesel content.
The left panel of Figure 8 shows the PM emissions. At low load,
there is no important PM reduction of ethanol blends with respect
to diesel, but at high load, a significant decrease with biofuel blends
is observed. Different from the opacity results, EBD presents the
highest reduction in PM emission. This can be explained because
THC emissions from ED17 are much higher than with the other
fuels (the probability of adsorption/condensation onto the surface
of soot particles is higher). Such an increase partly compensates
the significant reduction in opacity obtained with this blend.
The volatile organic fraction (VOF) with the blends tested
increases as the ethanol content in the blends becomes higher
(Figure 9). This result confirms that the increase in adsorbed/
condensated HC is higher than the soot reduction (the latter
derived from the opacity measurement).
Particle size distributions of tested fuels corresponding to
C0 and H engine modes are shown, as examples, in Figure 10.
No clear tendency can be found in the ethanol blends
because, while the ED7.7 blend presents distributions similar
to reference fuel in both modes, the number concentration of
particles of EBD is lower than that of diesel fuel. The size
distribution obtained from the blend with the highest ethanol
content is composed of two modes: the accumulation mode,
which is the characteristics of diesel particles (composed of
soot and adsorbed THC), and the nuclei mode, which
indicates the presence of condensed hydrocarbon drops.
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Lapuerta et al.
The parameters derived from particle size distribution that
are generally used for quantification are the mean diameter
and total concentration (Figure 11). Although ED17 pre-
sents a nuclei mode, in these figures, only the results corres-
ponding to the accumulation mode have been used to
compare with the rest of the fuels. The mean diameter (dm)
decreases as the ethanol content in the blends increases.
ED7.7 and EBD show similar values of mean diameter, with
the effect of biodiesel on this parameter being negligible. The
reduction of the mean diameter obtained with EBD and
ED7.7 is due to the sharp decrease of large particles.
Although the nuclei mode has not been taken into account,
the mean size of the particles emitted with ED17 is even much
lower than that corresponding to the other fuels.
The trends obtained with the particle number concentra-
tion (PNC) are different from those obtained with the mean
diameter. While the PNC obtained with ED7.7 is similar to
that with reference fuel, the results corresponding to EBD
and ED17 are lower than that from diesel fuel. No important
differences in accumulation PNC can be found between these
two fuels.
8.4. Effect of Fuel Oxygen on Engine Emissions. It is well-
known that the oxygen presence in the fuel composition
favors the reduction of opacity and PM. However, there is no
clear tendency in THC, NOx, and CO emissions with oxygen
fuel (especially with ethanol blends), and there is almost no
literature about the particle size from blends with alcohol.
In this paragraph, the influence of fuel oxygen in emissions
is studied. While in the previous figures, the x axis repre-
sented the bmep values, in the following figures, the oxygen
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m Lapuerta et al.

Figure 12. THC and NOx variation rates.

Figure 13. Smoke opacity and PM variation rates.

fuel content is represented in this axis. In all cases, the y axis

represents variation rates, defined as variations in percentage
with respect to the emissions from diesel fuel. In each studied
emission, each fuel is represented by two points, correspond-
ing to low and high loads. Low-load conditions indicate the
mean variation results of U10 and C, and high load corres-
ponds to the average of F, G0 , and H. This type of repre-
sentation permits us to distinguish whether the engine load
has any significant effect or not. Two line types are drawn to
distinguish between the oxygen provided by biodiesel and
ethanol, with the continuous line corresponding to the
ethanol effect and the dashed line indicating the biodiesel
effect. The fuels tested are identified, for clarity, just in the
left panel of Figure 12.
The variation of gaseous emissions with the oxygen con-
tent is shown in Figure 12. The oxygen presence in the fuels Figure 14. VOF variation rate.
favors higher oxidation of the hydrocarbons remaining from
the combustion process. The results shown in Figure 12 with with diesel fuel. Although the oxygen presence and the lower
ED7.7 and EBD are similar to those obtained with diesel cetane number (derived from the addition of ethanol) favor
fuel, while ED17 presents much higher THC emissions. NOx formation, the results show a slight decrease in this
Therefore, oxygen is not the only parameter affecting THC emission. This can be explained because the adiabatic flame
emissions. The higher heat of vaporization of ethanol re- temperature is much lower for ethanol and because the heat of
duces the local combustion temperature, thus leading to vaporization of ethanol is much higher, with both effects
increasing incomplete combustion.16,31 These effects could counteracting the previous ones and leading to slight reductions
compensate each other for low ethanol and biodiesel of NOx emissions with respect to those from diesel fuel.36
presence not affecting THC emissions, while a significant Figure 13 shows the smoke opacity and PM emissions,
increase of the emitted hydrocarbons is obtained for a higher respectively. The higher the ethanol content, the higher the
ethanol content, especially at high load.
In the case of NOx emissions (left panel of Figure 12), the (36) Can, O.; C-elikten, I.; Usta, N. Energy Convers. Manage. 2004, 45,
results obtained with the blends are slightly lower than those 2429–2440.
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Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Figure 15. Mean diameter (dm) and particle number concentration (PNC) variation rates.
reduction in opacity, in both load conditions (except ED7.7
in low load). In this case, the effect of oxygen fuel in opacity is
very significant. However, the reduction observed is not
linear with the oxygen content, with the e-diesel blends
presenting higher opacity reduction for the same oxygen
content. This result indicates that the oxygen provided by
ethanol is more efficient than the oxygen corresponding to
biodiesel, trends in agreement with other authors.37 It can be
concluded that the reduction in opacity does not only depend
upon the fuel oxygen content but also the functional group
providing the oxygen atoms.
In the case of PM emissions, the trends are not so clear
as in opacity. While with ED7.7 and EBD blends lineal
reductions are obtained for PM emissions for increasing
oxygen content, the results obtained with ED17 do not
follow this trend; they show higher PM values than the other
blends. The high THC emissions observed with this blend are
probably contributing to its higher particle matter emissions.
Therefore, although oxygen favors PM reduction, some fuel
properties (volatility and heat of evaporation) should be
taken in account to explain this emission. This is in agree-
ment with some authors that consider that, from 20%
ethanol content onward, PM reductions are not observed
any more.31
The VOF values obtained with oxygenated blends are
higher than the diesel one, as observed in Figure 14. The
VOF values corresponding to ED17 are consistent with its
high THC emissions. The VOF increase is not linear with the
increasing fuel oxygen content. In this case, the oxygen
provided by ethanol favors a higher VOF increase than that
provided by biodiesel.
The variations corresponding to dm and total PNC are
shown in Figure 15. Some dm reduction was obtained with
every other fuel tested, with these reductions being higher at
high-load conditions. The dm corresponding to the ED17
blend is lower than that from EBD at high load. Therefore,
the fuel oxygen provided by ethanol favors higher dm
reductions than those provided by biodiesel. This can be
explained by the reduced agglomeration derived from the
lower soot concentration, corresponding to the lower smoke
opacity observed (left panel of Figure 13). Again, the reduc-
tion obtained is not linear with the oxygen content.
The left panel of Figure 15 shows the total PNC results
with respect to the fuel oxygen content. The results indicate
(37) Pepiot-Desjardins, P.; Pitsch, H.; Malhotra, R.; Kirby, S. R.;
Boehman, A. L. Combust. Flame 2008, 154, 191–205.
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that, while the blend with the lowest oxygen content presents
similar values to the reference fuel, the values corresponding
to blends with a higher oxygen content are significantly
lower. Therefore, although no linear trend was observed
for PNC with the oxygen content, it is clear that high oxygen
fuel composition favors the reduction of the total PNC
emitted and the differences between fuel oxygen derived
from ethanol or biodiesel are small.
9. Conclusions
The effect of biodiesel on the stability of e-diesel blends
and the engine performance and emissions using different
ethanol blends has been studied. The main conclusions are the
following: (1) The phase separation process of e-b-diesel
blends generates different types of unstable blends: two liquid
phases, a gelatinous interphase, or the formation of a gelati-
nous phase in the bottom of the cell glass. The composition of
the blend (ethanol and biodiesel content) and the temperature
are the factors that have some influence on the type of phase.
(2) Biodiesel fuel acts as a stabilizing component in e-diesel
blends, but at low temperatures and with high ethanol con-
tent, it favors the appearance of a gelatinous phase. (3) The
higher the ethanol content in the blend, the higher the THC
emissions and VOF, while smoke opacity shows the opposite
trend. With regard to NOx emissions, PM, and PNC, no clear
trend was found when the ethanol content increases in the
blends. (4) The variation of different emissions with respect to
fuel oxygen content is not linear. Although ED17 and EBD
present the same oxygen content, the results obtained with
both fuels are different in most of the emissions. Therefore, it
can be concluded that the effect of biodiesel or ethanol
addition is different. (a) When the ethanol content is high,
its higher heat of vaporization (with respect to diesel fuel)
leads to increases in the hydrocarbons remaining from the
combustion, thus becoming the main cause for the high THC
emissions with ED17. (b) The opacity reduction obtained with
ED17 is much higher that that corresponding to EBD, thus
indicating that the oxygen provided by ethanol is more
efficient that the oxygen provided by biodiesel. This trend is
opposite in PM emissions (the emissions obtained with ED17
are higher than those obtained with EBD) because of the high
THC emissions of the ED17 blend. (c) The blend with the
highest ethanol content presents a nuclei mode because the
high THC emissions favor the nucleation of hydrocarbons.
The mean particle diameter corresponding to the accumula-
tion mode of ED17 is lower than that obtained with EBD.
Energy Fuels 2009, 23, 4343–4354 : DOI:10.1021/ef900448m
Therefore, the effect of fuel oxygen on the particle size
depends upon its functional group.
Acknowledgment. The authors gratefully acknowledge the
financial support provided by the Spanish CDTI (research
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Lapuerta et al.
project CENIT 2007-1031, IþDEA) and by the company
Abengoa Bioenergy S.A. The companies Repsol and Nissan
are also acknowledged for the supply of the reference and
biodiesel fuels and for the donation of the engine tested, respec-
tively.