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Applied Energy 135 (2014) 450–460

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Hybrid biofuels from non-edible oils: A comparative standpoint with

corresponding biodiesel
Plaban Bora a,⇑,1, Lakhya Jyoti Konwar a,⇑,1, Jutika Boro a, Mayur Mausoom Phukan b, Dhanapati Deka a,
Bolin Kumar Konwar b
Biomass Conversion Laboratory, Department of Energy, Tezpur University, Tezpur 784028, Assam, India
Department of Molecular Biology & Biotechnology, Tezpur University, Tezpur 784028, Assam, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Non-edible oil based hybrid biofuels.

 Natural surfactant based hybrid fuel
systems (FFA, mono, diglycerides).
 Improved cold flow properties in
comparison to corresponding
 Future energy utilities.

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

Article history: Exploration of new non-edible feedstocks for biofuel production and the use of economically favorable
Received 13 May 2014 conversion technologies could significantly contribute to bioenergy research. In this regard the present
Received in revised form 21 August 2014 investigation aims to highlighten hybrid biofuels (HBFs) prepared from crude vegetable oils of five locally
Accepted 31 August 2014
available plant species namely, Gmelina arborea Roxb (GAO), Mimusops elengi Linn (MEO), Acer laurinum
Hasskarl (ALO), Thevetia peruviana Schum (TPO) and Mesua ferrea Linn (MFO). This new approach does
not involve any chemical reactions and can substantially reduce the production cost of vegetable oil
based biofuels. Besides, the HBF systems prepared here can be 100% renewable as they only contain
Non-edible oils
Hybrid biofuels
vegetable oil, butanol and ethanol, all products derived from biomass. The naturally occurring mono-,
Biodiesel di-glycerides and free fatty acid (FFA)s in crude vegetable oils (or esters in pretreated oils) functioned
Viscosity as surfactants in the formulation of stable fuel systems. The fuel properties of the formulations were
affected by the concentrations of these compounds in the vegetable oil. The optimum formulations
(oil:butanol:ethanol ratio of 60:30:10) exhibited viscosity (4.7–5.4 mm2/s), density (0.86–0.88 gm/cm3)
and gross calorific values (38.91–39.18 MJ/kg) comparable with their corresponding fatty acid methyl
esters (FAMEs). Moreover, they show superior cold flow properties than FAMEs. The present investigation

⇑ Corresponding authors. Tel.: +91 3712 275305.

E-mail addresses: bncplaban@gmail.com (P. Bora), lakhya07@gmail.com
(L.J. Konwar).
These authors contributed equally in designing, conducting experimental work
and writing the manuscript.

0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
P. Bora et al. / Applied Energy 135 (2014) 450–460 451

suggests that non-edible oil based HBF systems formulated in the study containing ‘bio-based’ and ‘green’
surface active agents in the system offers economically attractive candidature for the future biofuel
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction drastic reduction in the emissions of thermal NOx, CO, black smoke
and particulate matter [8–11]. Microemulsions are classified in
Due to increasing concerns over fossil fuels utilization, the use terms of Winsor system of classification and the same could also
of vegetable oils for production of biofuels has gained significant be extended to the HBFs due to their obvious structural similarities
importance in recent years. But the major impediments in success- [7]. Formulation of microemulsions are greatly influenced by the
ful commercialization of vegetable oil based biofuels like biodiesel properties of surface active agents and they are the ‘key compo-
are high feedstock cost (accounting for nearly 80% of the total cost) nents’ which play the most crucial role in converting the system
and conversion technology needed to reduce viscosity. Neverthe- from one Winsor type to another. Generally, the most ideal sys-
less, the right choice of raw materials as well as the method for tems of HBFs formulations are the Winsor Type IV, a single phase
production of vegetable oil based transportation fuels must always system in which the polar (water or alcohol or aqueous alcohol)
rely on techno-economical aspects. With the global demand for phase is completely dispersed in reverse micelles occurring in
renewable biofuel gearing up, the exploration of feedstock for pro- the oil phase. On the other hand, the systems are classified as Win-
duction of biofuels is both essential and critical. The judicious sor Type II (a two phase system) if the polar phase is not com-
exploitation of newer non-edible feedstock is imperative which pletely dispersed in the oil continuum [3–17].
will undeniably serve as an incremental step for addressing the Steady development in this area of fuel research has been wit-
long recognized problem of energy supply and simultaneously also nessed in current years. However, still there is paucity of scientific
support further research endeavors related to green chemistry, information pertaining to vegetable oil based HBFs (many dating
feedstock biology and bioenergy research [1,2]. The use of vegeta- back to 1980–1990s). Most of these studies dealt with either ‘alco-
ble oils as fuel is not new. Idea of using vegetable oils as fuel dates hol-diesel-surfactant system’ or ‘alcohol-vegetable oil–diesel-sur-
from the days of the diesel engine. However, their use thus far has factant systems’. Although, such fuel formations exhibit
been restricted by inherently higher viscosity. The high viscosity of properties comparable/superior to diesel, but in reality these com-
crude vegetable oil reduces fuel atomization and increases pene- plex systems do not confer to the broad objectives of biofuel
tration which in turn contributes to the formation of engine depos- research owing to use of non renewable components and hazard-
its, piston ring sticking, injector coking, and thickening of oil. ous surface active agents. These complex systems comprising mix-
Several methods are there to reduce the viscosity of vegetable oils tures of different externally added surface active agents increase
such as dilution (blending), microemulsification, pyrolysis (ther- the cost of fuel preparation. Besides, their use in engines may also
mal cracking), and transesterification [3–6]. Among these contribute to corrosion problems and green house gas (GHG) emis-
approaches transesterification is the most sought after process sion [18]. Some of the NOx/SOx producing surface active agents
for reducing viscosity of vegetable oils. However, requirement of used in previous studies include: 2amino-2-methyl-l-propanol,
longer reaction time, high energy input during biodiesel purifica- ethoxylated mono- and di-nonylphenols [19], N.N-dimethyletha-
tion steps, and formation of by-product in the form of glycerol nolamine [19], triethyl amine [15], trialkylamine [9], sodium bis-
makes the whole process expensive, time consuming, labor inten- 2-ethylhexyl sulfosuccinate [20], sodium 2-(2-dodecyloxyeth-
sive and economically less attractive. In addition biodiesel is pla- oxy)ethyl sulfate and coconut fatty acids diethanolamide [21],
gued by storage fouling, poor cold flow properties and increased dodecylamine [22], sodium bis(2-ethyl) dihexyl sulfosuccinate
NOx emission in comparison to petrodiesel [7]. [23], oleyl amine [24], 2-ethylhexylnitrate [24].
A viable alternative approach which can reduce process eco- Considering the disadvantages like corrosion and GHG emis-
nomics in this regard can be the mixing/blending of vegetable oil sions, the use of ‘bio-based’ surface active agents free from sulfur,
or diesel with polar low molecular weight alcohols, in presence nitrogen, inorganics and acids must be given preference for HBF
of surface active agents (surfactants and co-surfactants) to improve formulation [18]. Consequently, research on eco-friendly surfac-
miscibility of polar and non polar oil phases. The process suffi- tant based microemulsions and HBFs has gained importance in
ciently reduces the interfacial tension between the dispersed or recent years. Sorbitan monooleate, alcohol ethoxylate (hydropho-
polar phase (e.g. ethanol) and continuous (oil) phases, resulting bic), polyisobutylene succinic anhydride ester of monomethyl-
in formation of hybrid biofuel (HBF) having physicochemical prop- capped poly(ethylene glycol) [25], glycerin and polyethoxy-ester
erties comparable to diesel and biodiesel (Scheme 1) [7–10]. Due to based surfactants [14], butanol [26–29] are some of the examples
the similarities of HBFs with microemulsions, this type of biofuel of such non-polluting surface active agents used for formulating
production method has also been termed as microemulsification. eco-friendly microemulsion fuels. However, there exists scope for
Microemulsion systems can be characterized by well dispersed further improvement through cost effective and environmentally
optically isotropic nano-sized fluid structures or colloidal disper- benign HBF preparation using vegetable oil and ‘bio-based’ surface
sions [4,11]. Though water has been predominantly used as polar active agents may be an attractive fuel option in the ensuing
phase for the formation of microemulsion, recent studies have also future.
shown successful application of ethanol as polar phase for formu- The presented research work investigates the feasibility of non-
lating hybrid fuel systems having aforementioned structural simi- edible oil based HBF as an economically attractive alternative to
larities with ‘microemulsions’ [3,7,24]. The advantages of this biodiesel. We report the formulation of a simple and cost effective
approach over the transesterification include lower production HBF system comprising of ‘crude vegetable oil–butanol–ethanol’
costs, short production time, simple and easy implementation which can be produced entirely from biomass sources (Scheme 1).
(on the farm blending) and no by-product formation due to non- The reported work also specifically highlightens the role of mono-,
involvement of chemical reactions. Besides, such fuels incorporat- di-glycerides and FFAs (or fatty esters) present in the crude
ing alcohols exhibit lower combustion temperature, which causes vegetable oils as naturally occurring surfactants for the formulation
452 P. Bora et al. / Applied Energy 135 (2014) 450–460

Route A:

Ethanol Butanol


Crude vegetable oil Hybrid biofuel (HBF)

Route B:
Methanol Ethanol Butanol

Esterification Mixing
60 C

Crude vegetable oil Low FAA vegetable oil Hybrid biofuel (HBF)

Scheme 1. Preparation of HBF from crude/non-edible vegetable oils.

of stable HBF. Butanol incorporated into the system was the only performed on a 250 mL three necked round bottomed flask in an
externally added surface active agent. Ethanol present in the sys- oil bath equipped with magnetic stirring at 65 °C. In a typical reac-
tem as dispersed phase also constituted a bio-based alternative tion, 100 g preheated oil was added to 100 mL 2% (v/v) methanolic
considering its possible large-scale production at relatively low cost H2SO4 stirred and heated to at 65 °C for 30 min. It was essential to
by fermentation [30]. Besides, to the best of our knowledge this is keep the reaction time to 30 min, to prevent transesterification
the first report of HBF preparation from GAO, MEO, ALO and TPO. (i.e. conversion of glycerides to a minimum) as it also removes
Among these, MFO, TPO and GAO have been previously reported the surfactants: mono- and di-glycerides present in oil. After com-
for biodiesel preparation whereas, MEO and ALO have not been pletion of the reaction, excess methanol was removed with a Stero-
reported for of any type of biofuel preparation till date. glass rotary vacuum evaporator (STRIKE202). The product was
neutralized with 1 M NaHCO3 solution, followed by washing with
2. Experimental 200 mL deionised water. The oil layer was recovered in a sapertory
funnel and dried over anhydrous Na2SO4 prior to use. The conver-
2.1. Materials sion of FFA to esters and glyceride content in the pretreated oils
were determined by GC according to ASTM D6584 method on a
Five indigenous oil bearing plant species of Assam, India TRACE™ 1300 (Thermo Scientific) gas chromatograph equipped
namely, Gmelina arborea Roxb, Mimusops elengi Linn, Acer laurinum with FID detector and Agilent (Select Biodiesel for glycerides) GC
Hasskarl, Thevetia peruviana Schum and Mesua ferrea Linn were column. The column temperature was held at 50 °C hold 1 min,
selected for the present study. Detailed descriptions of the selected 15 °C/min to 180 °C, 7 °C/min to 230 °C, 30 °C/min to 380 °C and
species are provided in (Supporting information, Table S1 and held for 5 min. Helium was used as the carrier gas at a flow rate
Fig. S1). Ethanol (<99.9%), Na2SO4 (99.5%), NaHCO3 (99%), Pyridine of 3 mL/min.
(HPLC grade), H2SO4 (98%), n-Hexane were purchased from Merck
India Limited, Mumbai. Butan-2-ol (Reagent PlusR, P99%), 1-buta- 2.4. Preparation of HBF
nol (anhydrous, 99.8%), n-Heptane (99.9%), Methyl heptadecanoate
(99%), N-methyl-N-(trimethylsilyl)trifluoroacetamide (98%), FAME HBFs were prepared by mixing the oils (pre-dried over anhy-
mix (Supelco, 37 component), ASTMÒD6584 Individual Standard drous Na2SO4) with butan-2-ol/1-butanol and ethanol in a 25 mL
Solution and Internal Standards Kit were purchased from Sigma beaker on a magnetic stirrer at room temperature. Butanol was
Aldrich. Refined edible-grade soybean oil was purchased from a used as co-surfactant. The resulting mixture was stored in glass
local supplier and dried over anhydrous Na2SO4. All chemicals bottles at room temperature (25 °C). Butanol was used in the fuel
and reagents were used without further purification. system due to its optimum hydrophilic lipophilic balance (HLB),
gross calorific value, cetane number and possible production from
2.2. Oil extraction biological sources [26,27]. The HLB number of butanol was calcu-
lated as:
Oil extraction was carried out by Soxhlet extraction method
HLB ¼ 20  ðM H =M H þ ML Þ ð1Þ
(AOAC 963.15., 1976) [31]. Excess solvent was removed with a
Steroglass rotary vacuum evaporator (STRIKE202). Oil content for where MH is the formula weight of hydrophilic portion of the mol-
each of the individual samples was expressed in weight percentage ecule and ML formula weight of the lipophilic (hydrophobic) portion
(with triplicates). Following solvent removal, the oil samples were of the molecule. The value was 4.59 for both 1-butanol and 2-buta-
centrifuged (Thermos-scientific, 5000 rpm for 15 min) to remove nol. This HLB number indicates the suitability of butanol for formu-
solid particles and impurities. The oil was finally stored in amber lating Winsor Type IV system with ethanol dispersed in oil based on
glass bottles for further experiments. arbitrary scale proposed by Graphin and Becher [32]. Addition of
external surfactants (ionic or non-ionic) were avoided in the pro-
2.3. Pretrement of crude vegetable oils cess as all the extracted vegetable oils contained significant
amounts of mono-, di-glycerides and free fatty acids (FFA) which
In order to reduce FFA content, the acid/crude vegetable oils function as surfactant in the preparation of HBFs [33]. Samples
were pretreated by esterification with methanol. Reactions were comprising of different volume fractions from each of the
P. Bora et al. / Applied Energy 135 (2014) 450–460 453

components (oil/butanol/ethanol) were formulated, visually employing a 4 mW He–Ne laser at wavelength = 632.8 nm, tem-
inspected (signs of turbidity, phase separation) for analyzing the perature 20 °C and detector angle 173° equipped with a thermo-
physical stability. Thermal annealing and centrifugation were also static sample chamber. The effect of varying the order of addition
carried out for further confirmation of physical stability. The phase of fuel constituents, stirring speed and oil pretreatment on droplet
behavior of each type of the vegetable oil based systems was repre- size distribution were also studied using light scattering measure-
sented by pseudoternary phase diagrams. ments. The refractive index of the samples was measured by a
For comparison the fuel properties of the corresponding FAME Rudolph J357 automatic refractometer. Prior to measurements,
(biodiesel) were estimated empirically from their fatty acid profiles samples were not subjected to any pretreatment such as filtration
using the equations suggested by Ramírez-Verduzco et al. [34]. The as it could transform the systems under high vacuum. All the sol-
details on the method are presented in the Experimental section of vents were filtered through 0.2 lm filter and the vegetable oils
Supporting information. were centrifuged (5000 rpm for 15 min) to remove all suspended
and particulate matter.
2.5. Physical stability of the fuel system
2.9. Determination of physicochemical properties
The physical stability of the fuel samples was studied by storing
samples in an environmentally controlled chamber at room tem- The physicochemical properties of the extracted vegetable oils
perature (25–35 °C) for 30 days. The samples were visually and the corresponding HBFs were determined by using standard
inspected on hourly basis for their physical appearances (signs of methods described in Table S2, Supporting information.
turbidity and phase separation). Temperature cycling was con-
ducted over 30 days starting from 5 °C to ambient (gradient of 3. Results and discussion
5 °C) for 24 h. Phase separation was inspected by regular centrifu-
gation at 7000 rpm for 60 min. The samples with no signs of phase 3.1. Fatty acid profile
separation after 30 days observation period were designated as
‘stable’ HBF systems [7–10,26]. The present work is an endeavor to investigate the feasibility of
non-edible oils as potential feedstocks for HBFs. The 1H NMR stud-
2.6. NMR spectroscopy ies confirmed the presence of triglycerides (a glycerol signals: m,
4.15 and 4.3 ppm and m, 5.2 ppm and b glycerol signal, t,
The oil samples were analyzed by 1H NMR spectroscopy to 2.34 ppm) as the main component along with variable amounts
detect the presence of triglycerides and fatty acids on a Jeol JNM- of fatty acids (t, 3.34 ppm) (Figures not shown) [35]. The details
ECS400 NMR spectrometer at 25.5 °C with CDCl3 as solvent and of the investigated feedstock are given in Table S1, Supporting
TMS an internal standard respectively [35]. The HBFs were also information. The fatty acid profile and the physicochemical proper-
analyzed by means of 1H NMR spectroscopy to detect any struc- ties of the reported oils have been presented in Tables 1 and 2
tural and chemical transformations during the process. respectively.
Fatty acid profile is of prime concern in determining the poten-
2.7. GC analysis tial of feedstock for biodiesel production. Important fuel parame-
ters like cetane number, calorific value, kinematic viscosity,
Fatty acid compositions were determined on a TRACE™ 1300 oxidation stability, iodine number etc of vegetable oil based fuels
(Thermo Scientific) gas chromatograph equipped with FID detector like biodiesel are directly affected by the fatty acid composition
and TRACE™ TR-FAME GC column. The methyl esters were pre- of the feedstock oil [34]. Table 1 shows the fatty acid composition
pared according to AOCS Official Method 1998; Ce 1e62 and Ce of the investigated non-edible oils determined by GC–FID. 1H NMR
2e66. The individual components were identified by comparison was not used for fatty acid profiling as it cannot be used to quantify
of retention times with the standard FAME mix and the wt% of the saturated acids individually and also gives erroneous results in
the individual fatty acids were calculated based on internal stan- the presence of mono- or di-acylglycerols in oil (Table 2) [35]. Oleic
dard (methyl heptadecanoate). The column temperature was held acid was the major fatty acid in MEO, TPO, and MFO; whereas
at 50 °C for 2 min, then heated to 200 °C at 10 °C/min then to
300 °C at 5 °C/min and finally held for 10 min. Helium was used Table 1
as the carrier gas at a flow rate of 1 mL/min. Fatty acid composition of the selected species.
The unidentifiable esters were identified by a GC–MS analysis in
Fatty acid (wt%) GAO MEO TPO ALO MFO
a Perkin Elmer Claurus 600 gas chromatograph equipped with DB-
Myristic (C14:0) – – 0.07 0.35 –
5 ms column. The MS was scanned from 50 to 600 Da. The column
Palmitic (C16:0) 5.62 27.62 21.15 27.11 12.85
temperature was held at 80 °C for 5 min, then heated from 80 °C to Palmitoleic (C16:1) – 0.26 0.19 1.48 0.15
300 °C and the rate of increase was 5 °C/min. The carrier gas used Stearic (C18:0) 5.38 10.75 7.87 2.49 11.81
was helium and the flow rate was maintained at 1 mL/min. The Oleic (C18:1) 33.99 48.52 43.44 12.96 49.3
glyceride content in the pretreated oils were determined by GC Linoleic (C18:2) 36.03 6.85 25.33 34.69 21.17
Arachidic (C20:0) 2.35 2.61 1.16 1.18 0.9
according to ASTM D6584 method on a TRACE™ 1300 (Thermo Sci-
Gadoleic (C20:1)a 10.84 0.87 0.15 – 0.58
entific) gas chromatograph equipped with FID detector and Agilent Heneicosanoic (C21:0) – 0.86 – – –
(Select Biodiesel for glycerides) GC column. The column tempera- Behenic (C22:0) 4.64 1.14 0.46 0.35 0.27
ture was held at 50 °C hold 1 min, 15 °C/minute to 180 °C, 7 °C/ Erucic (C22:1) 1.1 – – – 2.84
Ligoceric (C24:0) – 0.51 0.17 0.098 0.12
min to 230 °C, 30 °C/min to 380 °C and held for 5 min. Helium
CPFAb – – – 21 –
was used as the carrier gas at a flow rate of 3 mL/min. Saturated 18.01 43.49 30.88 50.13 25.95
Unsaturated 81.98 56.5 69.11 70.13 74.04
2.8. Dynamic light scattering (DLS) Polyunsaturated 36.03 6.85 25.33 34.69 21.17
Others 0.01 0.01 0.01 – 0.01
DLS measurements were conducted to investigate the droplet Based on GC–MS.
size distribution of the HBFs on a Nano S Malvern-instrument CPFA was determined using 1H NMR as % CPFA ¼ 150  ðACH2  =ACH3 Þ.
454 P. Bora et al. / Applied Energy 135 (2014) 450–460

Table 2
Physicochemical properties of the vegetable oils.

Property GAO MEO. TPO ALO MFO Refined soybean oil

Gross calorific value (MJ/kg) 39.45 39.42 39.43 39.08 38.83 39.12
Density (g cm3 @ 15 °C) 0.886 0.905 0.885 0.899 0.935 0.925
Kinematic viscosity at 40 °C (mm2/s) 21.32 28.12 27.06 24.73 38.34 31
Acid value (mgKOH g1) 16.13 14.02 13.34 5.17 16.1 0
Oxidation stability index (h) 1.86 5.57 6.45 6.15 3.22 n.d
Oil content in Kernels (wt%) 58 24 63 41 72 –
FFA (wt%) 8.10 4.94 6.70 2.56 8.09 –
Monoglyceride (wt%) 13.23 6.44 10.02 5.04 13.40 <0.2
Diglyceride (wt%) 11.79 14.31 8.36 3.70 11.10
Triglyceride (wt%) 66.72 70.70 74.79 86.56 62.52 99.8
Others (wt%) 0.16 3.05 0.13 2.14 4.78 –

linoleic acid in GAO and ALO. TPO had the highest amount of sat-
urates (34.17 wt%) followed by MFO (25.36 wt%) and MEO
(7.94 wt%), respectively. Interestingly, ALO contained, sterculic acid,
which is a cyclopropene fatty acid (CPFA). The presence CPFA was
confirmed by the appearance of characteristic –CH2– signal of the
cyclopropene ring at 0.76 ppm in 1H NMR of ALO and its fatty acid
methyl esters. The percentage of CPFA was estimated to be 21 wt%
using the expression: %CPFA ¼ 150  ðACH2  =ACH3 Þ; where,
ACH2  is the peak area of 0.76 singlet and ACH3 the peak area of
0.88 triplet (terminal CH3 of the fatty acid methyl esters) (Fig. 1)

3.2. Physicochemical properties of the oils Fig. 2. Appearance of extracted seed oils under visible light (1) GAO, (2) MEO, (3)
ALO, (4) TPO, and (5) MFO.
Vegetable oils of all the investigated species were bright to light
yellow transparent liquids with the exception of MFO (a dark
brown liquid) (Fig. 2). All the species exhibited variations with of high amounts of unsaturated fatty acids such as oleic, linoleic
respect to kernel size and oil content (oil content was >24% in all and linolenic acids results in lower viscosities while more saturated
the species). The oil content of the kernels and important physico- oils are solid at room temperature, e.g. lard, butter, coconut oil. The
chemical properties of oils are presented in Table 2. M. ferrea kernel low viscosity of ALO was attributed to the presence of CPFA and
had the highest amount of oil (72%) followed by T. peruviana (63%), unsaturated fatty acids as major constituents thereby resulting in
G. arborea (58%), A. laurinum (41%) and M. elengi (24%) respectively. the triacilglyceride chains avoiding their effective packing, due to
The viscosities of the oils were similar to those typically reported the lower inter- and/or intramolecular interactions of cycloprope-
for vegetable oils in the range 21–38 mm2/s. The viscosity of the oils noid ring in presence of CPFA [36,37]. The densities of the oils were
in the descending order is as follows: MFO > MEO > TPO > ALO > - similar to those typically reported for vegetable oils. Additionally,
GAO. The viscosities of respective vegetable oils varied due to dif- all the seed oils contained significant quantities of FFA, mono-
ferences in their fatty acid composition. Generally, the presence and di-glycerides (8.74–24.5 wt%). ALO contained 2.56 FFA wt%,



Normalized Intensity

Normalized Intensity



1.63 0.23
0.95 0.90 0.85 0.80 0.75
Chemical Shift (ppm)

α glycerol signal of triglyceride


β glycerol signal of triglyceride


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)

Fig. 1. 1H NMR patterns of ALO.

P. Bora et al. / Applied Energy 135 (2014) 450–460 455

whereas GAO and MFO contained more than 8 wt% FFA. The highest low while viscosity of HBF below the highlighted region was too
concentration of mono- and di-glycerides were also found in MFO high [41].
(13.4 wt% mono- and 11.1 wt% di-glyceride) followed by GAO From Table 3 it is also seen that HBF properties were mainly
(13.23 wt% mono- and 11.79 wt% di-glyceride) (Table 2). High influenced by oil source i.e. surfactant concentration (mono-, di-
unsaturation in the oil results in low storage stability and gum for- glyceride and FFA content) in vegetable oil, pretrement and
mation and presences of such components are reported to have oil:butanol:ethanol ratio while preparation conditions had little
adverse effects on fuel quality of biodiesel [34]. Generally, oils with effect. The presence of FFA in fuels is undesirable as it can cause
higher amount of saturated acids are less susceptible towards oxi- corrosion problems in engines. To address this issue the FFAs pres-
dation but on the flipside they tend to remain as solids at room tem- ent in the vegetable oils need to be removed. This was achieved by
perature due to more effective packing of fatty acid chains. Thus esterification of the oil with methanol prior to preparation of HBFs
saturated oils are less preferable for HBF preparation. Viscosity is (Section 1.3). Esterification effectively converted the FFAs present
also affected by fatty acid profile and the percentage of mono-, di- in crude seed oil into fatty ester (also a surfactant) [32,33] without
glycerides and FFA. Hence, due to the combined effect of variations affecting other surfactants; mono- and di-glycerides present in oil.
in these components a direct correlation was not observed between In this study, HBFs were also formed with esterified TPO and MFO
viscosity and percent unsaturated vs. saturated fatty acid. (P-HBF) as with the crude vegetable oils. For P-HBF samples with
oil (pretreated):butanol:ethanol ratio of 60:30:10, the fuel proper-
3.3. Formation of HBF ties were analogous (in some instances improved) in comparison
to the crude vegetable oil based systems, as in the case of pre-
3.3.1. Phase behavior of the fuel systems treated MFO (FFA <0.3%, 17% FAME 14.5% monoglyceride, 12.9%
The phase behavior of the five different natural surfactant based diglyceride, 55.3% triglyceride) and TPO (FFA <0.2%, 12.2% FAME,
fuel systems composing of vegetable oil, butan-2-ol and ethanol at 10.5% monoglyceride, 8.9% diglycerides, 68.2% triglyceride) respec-
room temperature are represented by pseudoternary phase dia- tively (Table 4). The increased heating values of P-HBF could be
grams (Fig. 3). A refined soybean oil based system was used as explained by the incorporation of more energy rich fatty esters into
the control. The shaded portion in the phase diagram represents the systems while, the reduced viscosity was most likely associ-
the ‘unstable’ formulations while the un-shaded portion represents ated with the change in overall geometry of the dispersed drup-
‘stable’ formulations. ‘Unstable’ formulations formed Winsor Type elets (Table 3 and 4) [42]. Nevertheless, for all pretreated
II system where excess ethanol had been expelled and accumu- vegetable oils a similar phase behavior was observed (Figure not
lated in a separate phase due to the inability of the surface active shown) as Winsor Type IV system was always formed at oil:buta-
agents present in the system to emulsify them, while ‘stable’ for- nol:ethanol ratios similar to crude vegetable oil based systems.
mulations formed Winsor Type IV system (single phase system)
(Fig. 4). The effect of natural surfactants (mono-, di-glycerides 3.3.2. Dynamic light scattering measurements (DLS)
and FFA) on HBF formations could be clearly seen from the six To confirm formation of nano-sized fluid microstructures, drop-
phase diagrams; showing a gradual reduction of the area of shaded let size distribution of HBF systems with oil:butanol:ethanol ratio
region (two phase) with the increasing concentration of these sur- of 60:30:10 and 60:20:20 were studied by DLS measurements
factants in the vegetable oils. Presence of these surfactants in the using TPO based systems. TPO systems were used as the reference
oils was vital for formation of Winsor Type IV systems between as it possessed intermediate chemical composition among the five
oil and alcohol. However, the presence of strong intramolecular species. The results showed the presence of dispersed droplets
H-bonds within the diglycerol head group increases the polar part having diameter in the range 1–150 nm in both the systems,
volume that causes reduction of hydrophilicity and HLB in compar- thereby confirming the formation of nano-sized fluid structures
ison to monoglyceride. As a result monoglyceride is a better emul- or microemulsion systems (Fig. 5(a)). Based on DLS measurements,
sifier than diglyceride [32,33,38,39]. Therefore, the presence of the average droplet size was estimated to be 21 nm in the 60:30:10
higher amount of monoglyceride is more desirable in the system. formulation, where as it was found to be 38 nm in the 60:20:20
In this study, the concentration of monoglyceride in the seed oils formulation (Table 3). This indicated that increasing the fraction
was found to be usually higher than di-glyceride with the excep- of ethanol in formulations leads to an increase in radii of the drop-
tion of MEO, which contained 6.44 wt% mono- and 14.31 wt% di- lets for a given oil fraction. Such change can be attributed to an
glyceride respectively. From Fig. 3 it was observed that only 1.2% increase in the mean curvature of surface active agent film thereby
of ethanol could be blended with refined soybean oil (<0.2% resulting in formation of larger droplets. Further increase in etha-
mono-, di-glyceride and FFA, used as control) without addition of nol fraction would result in conversion of Winsor Type IV system
co-surfactants. Whereas it was possible to blend up to 7%, 11%, to Winsor Type I system via Winsor Type II and Winsor Type III
14.3%, 16.7% and 18% ethanol in ALO, MEO, TPO, MFO and GAO (bicontinuous) systems. Such structural variations of microemul-
respectively. This variation of formulations which was necessary sion systems with amount of polar phase fraction (e.g. water) in
for formation of single phase HBF samples signifies the role of the system have been elaborately discussed in previous studies
mono-, di-glycerides, FFA as surfactant in these systems. However, [42]. The observed difference in droplet size of different formula-
there is always an optimum amount of surfactant which is neces- tions could be the origin of variations in fuel properties of the
sary for high stability of the final system. Previously, the stability of aforesaid formulations as also reported for commercial diesels
the formulated HBF systems was reported to be influenced by the based microemulsion fuels [22].
nature of co-surfactant used (chain length) and the ratio of co-sur- To evaluate the effect of pretreatment, droplet size distribution
factant to ethanol. However, in the present study both 1-butanol of esterified TPO based systems were similarly investigated by
and butan-2-ol were found to perform equally well (identical light scattering measurements (Fig. 5(b)). The effect of mixing
hydrophilic lipophilic balance, Section 2.4), (Table 3) [8–10]. None- order of components and variation of stirring time, speed were also
theless, we conducted rest of our study with butan-2-ol due to its studied by light scattering experiments on samples prepared under
better ability to inhibit the formation of liquid crystals and its varying conditions. The density, viscosity and calorific value of
lower solubilization/solvent effect [40]. Also, from the view of fuel these samples were also determined and presented in Table 3.
properties the formulations within the highlighted region of the Interestingly, the average droplet sizes of the pretreated oil based
phase diagrams were suitable in terms of fuel properties (Fig. 3). systems were much lower and in the range 1.7–1.8 nm, similar
The energy content of HBFs above the highlighted region was too to diesel-ethanol microemulsion based fuel system [22]. The
456 P. Bora et al. / Applied Energy 135 (2014) 450–460

Fig. 3. Pseudoternary phase diagrams of the various natural surfactant based systems of vegetable oil, butan-2-ol and ethanol at room temperature; (a) Refined soybean oil
(0% natural surfactant), (b) ALO (11.39% natural surfactant), (c) TPO (25.08% natural surfactant), (d) MEO (25.65% natural surfactant), (e) GAO (32% natural surfactant) and (f)
MFO (33.12% natural surfactant). The Winsor type IV regions within the circles represent formulations suitable for fuel applications (HBF).

reduced droplet sizes and narrow distributions were possibly stirring time which confirms the formation of self organized
caused by the incorporation of methyl esters into systems, which systems.
have higher HLB than their corresponding FFA. For example, HLB
of oleic acid is 2.34 where as HLB of methyl monooleate is 3.16 3.3.3. NMR study
(calculated using Eq. (1)). Generally, increasing HLB of surface The 1H NMR patterns of TPO based HBF clearly shows the char-
active agent corresponds to increasingly hydrophilic nature and acteristic glyceridic signals (not found in biodiesel) thereby con-
causes structural modification to the system [39,42]. The firming the non-involvement of chemical reactions (Fig. 6). Due
decreased concentration of triglycerides and diglycerides may also to incorporation of alcohols several additional peaks and chemical
have contribution to this effect. However, no momentous shifts were also observed, the CH peak of butan-2-ol appeared at
variations in the droplet size, kinematic viscosity, density or gross 3.4 ppm (multiplet), while the multiplet near 3.6 ppm was
calorific value were observed with variation in order of mixing and assigned to the CH2 peak of ethanol.
P. Bora et al. / Applied Energy 135 (2014) 450–460 457

Alcohol phase Oil phase

Alcohol phase Oil phase

(a) (b)

Winsor Type II Winsor Type IV

Winsor Type II

Fig. 4. (a) Separation of Winsor Type II system (obtained for refined oil) and (b) Comparison of a Winsor Type II system with a Winsor type IV system (obtained from crude
MFO) after 30 days storage.

3.3.4. Fuel properties of optimum formulations concentration of surfactants (mono-, di-glycerides and FFAs or
Table 4 presents the density, viscosity and gross calorific values esters of FFAs) in the vegetable oils. The vegetable oil with high
of the optimum HBF (those exhibiting properties closest to biodie- surfactant concentration usually formed HBF with lower viscosity
sel) prepared from five vegetable oil feedstock at the ratio 60:30:10 and density. The viscosity of the HBFs in the descending order
in comparison to corresponding biodiesel. The fuel properties was as follows: ALO > MEO > TPO > MFO > GAO; showing the grad-
(density, viscosity, gross calorific value) of 1-butanol, 2-butanol, ual improvement in flow properties with the increasing concentra-
ethanol, pretreated TPO and pretreated MFO were also presented tion of surfactants in the respective vegetable oils. This could be
in Table 4. The 60:30:10 formulations were considered as they due to decrease in average molecular weight of vegetable oils with
were the most stable Winsor Type IV formulations exhibiting fuel increased concentration of the surfactants. The densities and vis-
properties closest to biodiesel within the highlighted region in cosities of the HBFs reported in this study were much lower than
Fig. 3. Moreover, our previous work with MFO–butanol–ethanol those typically reported in previous literature [8–10]. This is
HBF showed that systems containing less than 60% (v/v) oil (i.e. because most studies in literature only dealt with refined vegetable
formulations with oil:butan-2-ol:ethanol ratio 50:40:10) exhibited oil based systems. Whereas, systems reported here were complex
low calorific value (37.24 MJ/kg), while those with more than 60% systems made up of large fractions of low molecular weight com-
(v/v) (i.e. formulations with oil:butan-2-ol:ethanol ratio 70:20:10) ponents such as FFAs (or their esters), monoglycerides and diglyce-
were more viscous (viscosity P18.42 mm2/s at 20 °C), rendering rides which also functioned as surfactants.
them incompatible for application in diesel engines [41]. From HBF systems are expected to exhibit superior cold flow proper-
Table 4 it is observed that fuel properties were also influenced by ties in comparison to biodiesel on account of presence of alcohols
the composition (chemical structure) of the parent vegetable oil. which can function as antifreezing agents. Deka and Basumatary
The properties of HBF formulations were mainly affected by the [43] and De and Bhattacharyya [44] reported the pour point of

Table 3
Effect of formulation conditions on HBF properties.

Oil:butanol:ethanol Order of mixing of components Conditionsa Kinematic viscosity at Density at 20 °C Gross calorific value Average droplet
(left to right) 40 °C (mm2/s) (gm/cm3) (MJ/kg) size (nm)b
60:30:10 Oil:2-butanol:ethanol 15 min 5.44 0.878 38.91 22
60:20:20 Oil:2-butanol:ethanol 15 min 6.93 0.882 38.81 38
60: 30:10 Oil:1-butanol:ethanol 15 min 5.4 0.877 – –
60*:30:10 Oil:2-butanol:ethanol Gentle 4.73 0.860 39.18 1.6
60 :30:10 Oil:ethanol:2:butanol Gentle 4.72 0.860 – 1.6
60 :30:10 Oil:2-butanol:ethanol 30 min 4.73 0.860 39.18 1.7
60*:30:10 Oil:2-butanol:ethanol 60 min 4.73 0.860 39.18 1.7
60c:30:10 Oil:2-butanol:ethanol 15 min 9.94 0.879 – –

All experiments were conducted using crude TPO except sample marked 
and c.
Stirring speed was fixed at 150 rpm.
Based on DLS measurements.
Refined soybean oil.
Pretreated/esterified vegetable oil (Section 2.3).
458 P. Bora et al. / Applied Energy 135 (2014) 450–460

Table 4
Selected fuel properties of HBF in comparison to corresponding biodiesels and components comprising the system.

Species Fuel type Density at 20 °C (g/cm3) Kinematic viscosity at 40 °C (mm2/s) Gross calorific value (MJ/kg)
MFO Biodiesel 0.872 4.654 39.85
HBF 0.895 5.16 38.88
P-HBF 0.877 4.97 38.94
ALO Biodiesel 0.875 4.41 39.79
HBF 0.873 6.85 38.67
TPO. Biodiesel 0.871 4.518 39.74
HBF 0.878 5.44 38.91
P-HBF 0.86 4.73 39.18
GAO Biodiesel 0.876 4.73 39.96
HBF 0.87 4.98 38.79
MEO Biodiesel 0.873 4.646 39.89
HBF 0.876 5.47 38.36
Refined soybean oil Biodiesel 0.876 4.28 39.78
HBF 0.879 9.94 38.62
1-Butanol – 0.810a 2.54a 29.20
2-Butanol – 0.807a 3.70a 29.20
Ethanol – 0.796a 1.19a 19.60
Pretreated TPO – 0.882 17 39.57
Pretreated MFO – 0.918 15 39.39

P-HBF = Prepared from esterified/pretreated vegetable oil.

At 15 °C.

14 (a)
14 Oil-Butanol-Ethanol (gentle shaking)
12 60:30:10 = Oil:butanol:ethanol Oil-Butanol-Ethanol (15 min stirring)
60:20:20 = Oil:butanol:ethanol Oil-Butanol-Ethanol (30 min stirring)
Distribution/ a.u

Distribution/ a.u

10 Oil-Butanol-Ethanol (45 min stirring)

8 Oil-Butanol-Ethanol (60 min stirring)
8 Oil-Ethanol-Butanol (gentle shaking)
4 4

2 2

0 0

0 100 200 300 8000 10000 0 4 8 12 8000 10000

Diameter/ nm Diameter/ nm

Fig. 5. DLS patterns of (a) crude TPO based HBF prepared at varying oil:butanol:ethanol ratio (30 min stirring at 200 rpm) and (b) pretreated TPO based HBF prepared under
varying conditions (oil:butanol:ethanol ratio was fixed at 60:30:10, stirring speed was 200 rpm and the order of mixing of components is shown from left to right).

1.0 Y1_PROTON-1 microemulsion optimum.esp



Normalized Intensity





CH2 peaks of butan-2-ol (m)

CH2 peak of ethanol (m)

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)

Fig. 6. 1H NMR of TPO based HBF.

P. Bora et al. / Applied Energy 135 (2014) 450–460 459

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