Indian Journal of Chemical Technology

Vol. 19, March 2012, pp. 134-139

Comparative study of stability and properties of alcohol-diesel blends

Rakhi N Mehta1, Mousumi Chakraborty2*& Parimal A Parikh2*
1
Department of Chemical Engineering, Sarvajanik College of Engineering & Technology,
Surat 395 001, India
2
Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology,
Surat 395 001, India

Received 2 May 2011; accepted 13 January 2012

Present study deals with the blending of petro-diesel with ethanol and butanol, where biodiesel is added as an
amphiphile (surfactant) to stabilize the blends. It is observed from the experiments that butanol forms more stable blends as
compared to ethanol which has been justified by the backscattering profiles and droplet size distributions of the emulsified
blends. In order to ascertain the applicability of blends as fuel, physical properties such as density, kinematic viscosity, flash
point, cold filter plugging point and surface tension of most stable blends (both ethanol and butanol) have been determined
as per the ASTM standards. The quality of the blends is checked using copper strip corrosion and oxidation stability. Cetane
index is calculated using four variable equation method. Results suggest that all the properties are in accordance with the
stipulated standard values with the only exception of flash points.

Keywords: Backscattering profiles, Droplet size distribution, Physical properties, Stabilized blends

World today is swarming with people and their needs
for the petroleum products is increasing in leaps and
bounds. However, the increase in prices of diesel fuel,
stringent emission regulations, and foreseeable future
depletion of petroleum reserves make it necessary to
ponder on to the issue of searching the new
alternatives for fuel and to develop new technologies
such as common-rail system, fuel injection control
strategies, exhaust gas recirculation, fuel-related
techniques, and so on to meet demands for
environment and energy. Studies on alternative fuels,
especially renewable fuels, become very important
research areas among fuel-related studies. Nowadays
considerable attention has been paid to the
development of alternative fuel sources in various
countries, with particular emphasis on biofuels.
Over the past few decades, researchers have
investigated the use of different alcohols such as
ethanol and butanol as a blending agent in petro-
diesel1,2. Bioethanol is produced from bio-derived
materials such as sugar cane molasses or cassava root,
have lower production cost and is environment
friendly3. Ethanol can be used without much
modification in the diesel engine, but it has some
limitations of lower miscibility, which may cause
————————
*
Corresponding authors.
E-mail: mch@ched.svnit.ac.in; pap@ched.svnit.ac.in
phase separation as ethanol is immiscible in diesel
over a wide range of temperatures4. This instability of
blends may also be attributed to the higher affinity of
ethanol towards water, which promotes phase
separation5. As all the automotive fuels are required to
be in a clear, single-liquid phase which does not
undergo phase separation, surfactants or emulsifiers
are added to improve the stability of such blends6. A
group of researchers have worked on injection,
ignition and combustion of 10-20% ethanol-diesel
blends and concluded that in presence of additives the
blends remain stable and give almost same
performance as petro-diesel with reduced emissions7.
Another work was carried out to study the phase
behavior and miscibility of ethanol into diesel, which
concluded that aromatic contents and intermediate
distillate temperatures had a significant impact on
miscibility limits of the blending fuels8. Property
studies and engine performance of ethanol blended
fuels have given appreciable results when studied by
the current group of researchers9,10. Butanol has also
been used effectively as a blending agent with diesel
to clear blend bearing single phase11. When such
blends were fueled to a multicylinder CI engine, it
showed improvement in exhaust gas temperature and
brake thermal efficiency. Also the emissions of CO
and HC were drastically reduced12. In the current
study, biodiesel is added as an amphiphile
 MEHTA et al.: COMPARATIVE STUDY OF STABILITY & PROPERTIES OF ALCOHOL-DIESEL BLENDS 135

(emulsifier) forming micelles that have non-polar tail was contained in a cylindrical glass cuvette and
oriented towards diesel and polar head towards examined throughout its length for about 20 min. The
ethanol or butanol13. data of the percentage transmission and backscattering
Thus, the motivation of blending bioderived were obtained. The profile of backscattering (BS) was
ethanol and butanol to diesel along with biodiesel obtained as a function of the sample height (mm).
could be justified from the fact that its addition These profiles constituted the macroscopic fingerprint
improves the values of kinematic viscosity, reduces of the sample at a given time.
environmental pollution, strengthens agricultural Microphotographs of surfactant-stabilized blends
economy, creates job opportunities, reduces diesel (1 mL) were taken using Coslab (India) microscopic
requirements, and thus contributes in conserving a camera. Droplets sizes and size distribution of the
major commercial energy source. These blends were microemulsions were measured by Coslab software
tested for their physical stability and properties in package.
order to ascertain its aptness for using it as a fuel Physical properties of most stable blends were
substitute. determined and compared. Density, kinematic
viscosity and flash- and fire-points of the blends were
Experimental Procedure
determined using Anton Parr Densitometer [model
Certified diesel, 99.9% pure standard anhydrous
DMA 4500(Austria)], Herzog kinematic viscosity
ethanol (Merck make), n- butanol (99.9% pure, Merck
meter [model HCP 852 (Germany)] and closed-cup
India) and ethyl ester of Jatropha Curcas oil based
Pensky Martens apparatus [Herzog (Germany)]
biodiesel (local make) have been used for the study.
respectively. Cold filter Plugging point was
As per the procedure provided by the biodiesel
determined using Scavini CFPP apparatus (Italy).
supplier, the transesterification of Jatropha oil was
Surface tensions of blends were determined using ring
conducted using ethanol with optimum molar ratio
method with the help of Kluss T9 Tensiometer
(8:1) using the catalyst concentration of 1% KOH,
(Germany). In the ring method the liquid is raised
reaction temperature 70°C and reaction time 210 min.
until contact with the surface is registered. The
At the end of the reaction, the mixture was allowed to
sample is then lowered again so that the liquid film
settle overnight and crude glycerine (bottom) and
produced beneath the ring is stretched. The maximum
biodiesel (top) were separated and washed with water,
force is only determined exactly on this return
which was supplied after sand filtration.
movement and used to calculate the tension.
Initially in 100% diesel, ethanol was added in small
increments of 1% with simultaneous increase in These tests were performed in accordance with
biodiesel. The quantity of biodiesel was decided on American Standard of Testing Methods (ASTM)
the basis of its effectiveness in the blends. Biodiesel standards. All the tests were performed thrice in order
less than 5% did not provide a stable emulsion, to ascertain the reproducibility of results. The quality
whereas its concentration of > 25% did not made any of the blends was checked using copper strip
further improvement in the stability of the blends. It corrosion and oxidation stability. Cetane index was
was observed that butanol showed clear single phase calculated using four-variable equation method.
on splash blending therefore butanol upto 25% was
Table 1—Selected ethanol and butanol blends (vol %) for
blended easily in diesel. Ethanol also showed stability check
formation of microemulsions, hence the blends
Blend Biodiesel, % Ethanol/Butanola, % Diesel, %
containing 5% (vol) ethanol were identified for
checking the effect of change in biodiesel. Blend Ethanol blends
stability was analyzed on the basis of transmission B1e 10 5 85
B2e 15 4.25 80.75
and back scattering profiles obtained by scanning the B3e 20 4 76
samples using light rays of 880 nm wavelength in a B4e 25 3.75 71.25
Turbiscan classic MA 2000 (Formulaction, France) Butanol blends
apparatus. The ethanol and butanol blends checked B1b 10 5 85
for stability criteria are enlisted in Table 1. B2b 15 10 15
Dispersed microemulsion droplet size measurements B3b 20 20 60
were carried out within few minutes after splash B4b 25 25 50
mixing of ethanol blends. The sample to be analyzed a
For butanol blends.
136 INDIAN J. CHEM. TECHNOL, MARCH 2012
Results and Discussion
The blends were scanned from bottom (0 mm) to
top of the cuvette (60 mm) for a period of 20 min. The
back scattering (BS) profiles suggest that all the
butanol blends show superimposing curves justifying
its stability even at maximum substitution. Figure 1
shows the enlarged section of back scattering profile
of butanol and ethanol, which signifies that butanol
forms more stable blends as compared to ethanol
blend. In this profile left hand ordinate shows
percentage back-scattering, right hand ordinate
shows time in minutes and abscissa shows the
length (mm). Figure 2 shows that initially low
biodiesel concentration in the ethanol blends shows
non-superimposing curves, which signifies varied
emulsion droplet size and distribution. But increasing
the concentration of biodiesel (20% and 25%)
provides superimposed curves and better back
scattering profiles. These results suggest that at higher
amphiphile (biodiesel) concentration stable blends
with smaller droplet sizes are obtained. In order to
find out exact emulsion droplet size distribution in
blends, microphotographs of emulsions were analyzed
as shown in Fig. 3.
Emulsion size distribution
From microphotographs and microemulsion droplet
size distributions (Fig. 3), it is observed that the
dispersed emulsion is in the range 2-10 μm. The
variation in the droplet size denotes that with the
gradual addition of surfactant into the blends, they
become stabled with small sized droplet and almost
clear single phase. Smaller emulsions droplets result
into lower %BS, which supports the back scattering
data.
Fig. 1—Comparative view of backscattering profile of (a) butanol and (b) ethanol blends
Depending on the physical stability criteria
fulfillment two of the blends containing 5% ethanol
and butanol (B1e, B1b) were selected for testing fuel
properties.
Fuel blend properties
Properties of selected blends were determined as
per the ASTM/BIS standards. Densities of blends
show resemblance with that of pure diesel, depending
on the individual densities of pure components.
Viscosity affects the atomization of a fuel upon
injection into the combustion chamber, thereby
ultimately the formation of engine deposits. The
higher the viscosity, the greater is the tendency of the
fuel to cause such problems14. The kinematic
viscosities (KV) of ethanol and butanol blends show
minor increase in the values due to the presence
of biodiesel which is comparatively viscous. The
desirable range according to BIS standard is 2-5 cSt,
and the values of KV of blends justify the same. Flash
points of both the blends are low as compared to
virgin diesel due to the presence of low temperature
flashing ethanol and butanol which has flash points
13°C and 29°C respectively. During the use of
blended fuels in colder climates there is a possibility
of formation of solids and crystals which rapidly grow
and agglomerate due to the presence of saturated and
unsaturated fatty compounds, thereby clogging fuel
lines and filters causing major operatibility problems.
Hence, it is inevitable to determine the cold filter
plugging point (CFPP) of the blends for smooth cold
operation of engines. The CFPP of ethanol and
butanol blends are found to be -2°C and -3°C
respectively, which is much lower than the stipulated
values as per ASTM standards. Net heat of
MEHTA et al.: COMPARATIVE STUDY OF STABILITY & PROPERTIES OF ALCOHOL-DIESEL BLENDS 137

Fig 2—Backscattering profile of ethanol blends with increase in biodiesel %

Fig. 3—(a) Microphotograph of emulsions and (b) dispersed microemulsion droplet size distribution of B4e blend
138 INDIAN J. CHEM. TECHNOL, MARCH 2012

Table 2—Fuel properties

Parameter Density Kinematic Flash point Cold filter Net heat of Cetane Copper strip Oxidation Surface
At 15oC viscosity o
C plugging combustion index corrosion stability tension
g/mL at 40oC, cSt point, oC MJ/kg mg/10 mL mN/m
Diesel 0.835 2.12 66 13 43.5 46 Not worse than 2.5 27.9
1(a)
Butanol 0.810 3.64 29 -45 33 <15 - - 29
Ethanol 0.789 1.2 13 - 29.7 9 - - 25
Biodiesel 0.880 6 170 15 39.4 47 Not worse than 4.45 31.55
3(a)
B1e 0.816 2.3 <27 -2 42.3 40.375 Not worse than 2.32 28.9
1(a)
B1b 0.833 2.38 33 -3 42.565 44.55 Not worse than 2.335 29.2
1(a)
ASTM/BIS BIS:1448 D-445 D-93 BIS: 1448 D-240 D4737-96a D-130 D 2274-94 Ring method
standards [P: 32] [P: 110]

combustion was estimated using D 4868-90 ASTM
method. Since water, ash and sulfur contents of the
blends are found to be negligible, they are not
included in the estimation of heats of combustion
(Table 2). As both butanol and ethanol have lower
heating values, it marginally affects the net heat of
combustion of blends. Cetane indices (CI) which
determine the fuel burning properties are
determined using standard calculation method
(Table 2). The blends show decrease in their cetane
index due to the lower CI of virgin alcohols.
Nonetheless B1b blend shows better CI value as
compared to B1e blend, thereby suggesting better
combustion property and hence clean burning.
Corrosion is one of the biggest threats for any
compression engine, hence in order to determine
the corrosive nature of the blend, copper strip
corrosion test was performed. The blends were
subjected to the test for 3 h at 100°C and the results
are given in Table 2. Oxidation stability is an
important property for determining the sediment
content of the fuel when subjected to oxygenated
ambience at higher temperatures for longer period
of time. Because the blends studied contain
biodiesel, which is susceptible to slow oxidation
this test became inevitable15. According to the
ASTM the sediments produced during oxidation
stability test should be less than 2.5 mg/100 mL.
Both the blends fulfill the stipulated standards. Fuel
atomization is the first process encountered during
the combustion of fuels to increase the surface
area and hence the evaporation rate in a
compression ignition engine and is largely
determined by the fuel's viscosity and surface
tension16. The observations suggest that surface
tension marginally increases due to the presence
of biodiesel.
Conclusion
(i) The turbiscan plots (back scattering profiles)
show that butanol blend is more stable than ethanol
blend.
(ii) The blends show appreciable resemblance in
physical properties, such as density, viscosity, cold
filter plugging point, net-calorific values, cetane
index, copper strip corrosion, oxidation stability and
surface tension with that of the petro-diesel. Only the
flash points are reduced due to the presence of
alcohols in the blends.
(iii) On comparison, the butanol blend shows better
properties such as density, flash point and cetane
index as compared to ethanol blend.
(iv) Hence, if the cost of producing butanol could
be reduced or some more economical method of
production could be established, it could prove to be
most viable fuel blend for the future.
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