Accepted Manuscript

Winterization studies of different vegetable oil biodiesel

Sandhya K. Vijayan, Mary NaveenaVictor, Abinandan

Sudharsanam, Velappan Kandukalpatti Chinnaraj, Nagarajan
Vedaraman

PII: S2589-014X(18)30012-4
DOI: doi:10.1016/j.biteb.2018.02.005
Reference: BITEB 13
To appear in:
Received date: 6 January 2018
Revised date: 21 February 2018
Accepted date: 22 February 2018

Please cite this article as: Sandhya K. Vijayan, Mary NaveenaVictor, Abinandan
Sudharsanam, Velappan Kandukalpatti Chinnaraj, Nagarajan Vedaraman , Winterization
studies of different vegetable oil biodiesel. The address for the corresponding author
was captured as affiliation for all authors. Please check if appropriate. Biteb(2017),
doi:10.1016/j.biteb.2018.02.005

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT

Winterization studies of different vegetable oil biodiesel

Sandhya K.Vijayan, Mary NaveenaVictor, Abinandan Sudharsanam, Velappan

Kandukalpatti Chinnaraj, Nagarajan Vedaraman*

Chemical Engineering Division, Central Leather Research Institute, Adyar, Chennai-600

020, India.

PT
Corresponding author: nvedaraman@yahoo.co.in Tel: 00 91 9444907898

Orcid Id: https://orcid.org/0000-0002-8981-4865

RI
SC
NU
MA
E D
PT
CE
AC

1
 ACCEPTED MANUSCRIPT

ABSTRACT

At low temperature, the presence of oleaginous compound with fatty acids bound to

crystallize and cause operability problems with compression engines. In this present

investigation, seven different fatty acid methyl esters (FAMEs) biodiesel from vegetable oils

(such as sunflower, coconut, jatropha, rice bran, palm, neem and mahua) were prepared by

PT
transesterification and were analyzed by gas chromatography (GC). Winterization of these

synthesized biodiesel were carried out to find their usability at low temperatures (0ºC—20ºC)

RI
and the crystals formed were separated. Further, the differential scanning colorimetry (DSC)

SC
were employed to identify the onset of melting point of the biodiesel from vegetable oils. The

results showed that crystal formation was observed for various biodiesel except sunflower oil
NU
that recorded no crystal formation with minimum temperature of 0ºC. These findings suggest
MA

that biodiesel synthesized from sunflower can be used as such at low temperatures compared

to the other synthesized biodiesel from vegetable oil.

D

Keywords: Biodiesel, Temperature effects, Differential Scanning Calorimetry, FAME,

E

Winterization.
PT
CE

1. Introduction
AC

Overwhelming response towards clean energy utilization has provoked the interest towards

the use of biodiesel among the world. Biodiesel (derived from plant or animal bio resources)

is alternative fuel that can be blended with conventional fuels to use in compression ignition

engines (McCormick et al., 2006). Furthermore, biodiesel is highly advantageous compare to

conventional diesel that includes: high cetane characteristics, condensed emanation of NOx,

SOx, carbon monoxide, hydrocarbons and particulate matter, respectively (Kulkarni & Dalai,
2
 ACCEPTED MANUSCRIPT

2006). Additionally, emissions of biodiesel contain less pollutants, such as poly-aromatic

hydrocarbons compare to conventional fuel (Graboski et al., 2003; Karavalakis et al., 2009).

The preparation of biodiesel is usually carried out by transesterification with alcohol as a

catalyst and the reaction is shown in Figure 1. Meanwhile, the blending of biodiesel (B5-B20

(v/v)) with conventional fuels is the most commonly in practice and are highly recommended

for good engine performance and better exhaust emissions (Moser & Vaughn, 2010).

PT
However, it is observed that use of biodiesel (B100) despite of blending, resulted in

RI
substantial reduction of carbon monoxide and hydrocarbon emissions (Vedaraman et al.,

SC
2011). Despite these advantageous mentioned above, the major setback of biodiesel is the

cold flow properties that hinders the practical application (Bhale et al., 2009; Lee et al., 1996;
NU
Soriano et al., 2006). The occurrence of saturated fatty acid in biodiesel is crucial for

temperature explicit parameters. So, at low temperature the fatty acids tends to form cloud
MA

(cloud point -CP), semi solid fractions (pour point-PP) and forms crystals (cold filter

plugging point -CFPP) thereby clogging and blocking the flow of biodiesel to engines
D

(Rasimoglu & Temur, 2014). Hence, several methods such as winterization, anti-gel additives
E

and blending have been used to prevent the formation of crystals (Kreulen, 1976; Nainwal et
PT

al., 2015; Ooi et al., 2005). Among the methods, winterization is the economical and simple,
CE

which is carried by keeping the biodiesel under refrigeration for specific temperature and

decanting the liquid after crystal formation (Smith et al., 2010). Further, the crystallization
AC

process reduces the overall onset temperature which tends to use the biodiesel at lower

temperature without clogging (Gómez et al., 2002). The use of branched chain alcohol to

produce biodiesel has reduced the crystallization onset temperature (Tco) (Lee et al., 1995).

Various researchers have reported to reduce the saturated fatty acids in biodiesel using

blending and addition of agents. For instance, the saturated fatty acids have been eliminated

using three stages of winterization and achieved reduction in CFPP to −8 °C and exhibited 9

3
 ACCEPTED MANUSCRIPT

% loss of peanut biodiesel (Karavalakis et al., 2009; Pérez et al., 2010). However, the

saturated fatty acid content in biodiesel obtained from beef tallow post winterization was

73.38% compared to the initial value of 86.91% yielded at temp 16.3°C (Doğan & Temur,

2013). Similarly, winterization based on micro heat exchangers of biodiesel from waste

cooking oil (BWCO) exhibited reduction of CFPP up to -7°C and saturated fatty acids from

21.3% to 9.6% (Kerschbaum et al., 2008). Meanwhile, the use of additives in winterization of

PT
BWCO resulted in CFPP reduction from −10 °C to −16 °C (Cheong et al., 1998; Wang et al.,

RI
2014). The process of winterization with additives has significantly enhanced the biodiesel

SC
properties (Chastek, 2011; Joshi et al., 2011; Wang et al., 2014; Wang et al., 2011).

However, in the use of additive (ethylene vinyl acetate copolymer) with blending (20%) of
NU
BWCO the CP, CFPP and PP reduced by -12°C, -16°C and -18°C with respect to the pre

winterization (Cao et al., 2014). Despite these significance, the additives may also possess the
MA

ability to induce more toxicity to the emission from the biodiesel. It is very imperative, the

biodiesel produced by winterization without additive is more efficient economically and

D

environmentally. Furthermore, not much extensive studies have been recorded to identify the
E

crystallization under various temperature of winterization of biodiesel from vegetable oil.

PT

Hence, this study investigated the temperature effect on crystallization of transesterification

CE

biodiesel of seven different vegetable oils (sunflower, coconut, jatropha, rice bran, palm,

neem, and mahua) respectively. Further, the loss of biodiesel during winterization was
AC

identified and reported along with solid fraction of saturated fatty acids. The properties of

biodiesel viz., density (ρ), viscosity (υ), PP, CP, flash point (FLP) and fire point (FRP) were

evaluated as per the standard procedures. Furthermore, the fatty acid composition of different

biodiesel and crystallization onset temperature (TCO) was analyzed by gas chromatography

(GC) and differential scanning colorimetry (DSC).

4
 ACCEPTED MANUSCRIPT

2.Experimental

2.1.Materials

Commercial refined vegetable oil from coconut, sunflower, rice bran, palm and unrefined oil

derived from jatropha, neem and mahua purchased from local market (Chennai, Tamilnadu,

India). All the chemicals used in experiment were of analytical grade (S.D fine Chemicals,

PT
India).

RI
2.2.Transesterification process

SC
Biodiesel usually referred as (FAMEs) from refined vegetable oils were prepared by
NU
transesterifying with NaOH 0.5% (w/w) with respect to oil dissolved in CH3OH

(oil/methanol ratio of 1:9 on a molar basis) at 67°C to 70 °C for a period of 2 hours.

MA

Unrefined oils, were transesterified with acid catalysis using 0.5 % Conc. H2SO4 by weight

with respect to oil and 30 % by weight of methanol along with un-refined oils at a
D

temperature of 65-72°C for a period of 16 hours (Canoira et al., 2006; Van Gerpen, 2005).
E

After transesterification, the upper methyl ester layer was separated and washed with water to
PT

eliminate the residuals from biodiesel (Demirbas, 2007). The transesterification process took
CE

place in round bottom flasks (two necked) Liebig condenser in a heating mantle with

magnetic stirrer. Then the biodiesel was dried in oven at 105 °C (378 K) for 3 h to remove
AC

traces of moisture. The product yield (Eqn 1) was calculated on a mass basis and are

expressed below

𝑊𝑡 𝑜𝑓 𝑏𝑖𝑜𝑑𝑖𝑒𝑠𝑒𝑙
𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝑦𝑖𝑒𝑙𝑑 (%) = 𝑋 100 (1)
𝑊𝑡 𝑜𝑓 𝑜𝑖𝑙

2.3. Winterization

5
 ACCEPTED MANUSCRIPT

Winterization experiment was carried out on all the different biodiesel at samples at 20±1°C,

15±1°C, 10 ±1°C, 5±1°C, and 0±1°C, correspondingly for a minimum period of 12 hours

slightly modified from literature (Lee et al., 1996). It was done using a low temperature

chamber (ROSS FLEXER TER62 STM141F). Different biodiesel samples were weighed and

poured into flasks and kept inside the chilling unit (Sub Zero Cooling Instruments, Chennai,

India). Subsequently, the samples were transferred to the erlenmeyer flask using a dried filter

PT
paper and funnel. The filter paper and the crystals separated out with it were weighed for all

RI
biodiesel samples and the liquid separated out was also weighed (Eqn 2 & Eqn 3). This

SC
procedure was repeated thrice and average value is taken for all the temperatures for each of

the seven biodiesel.

NU
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝐶𝑟𝑦𝑠𝑡𝑎𝑙 𝑤𝑡. (%)) =
MA

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑖𝑙𝑑 𝑎𝑓𝑡𝑒𝑟 𝑤𝑖𝑛𝑡𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛

𝑋 100 (2)
𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑤𝑖𝑛𝑡𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
E D

𝐿𝑖𝑞𝑢𝑖𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝐵𝑖𝑜𝑑𝑖𝑒𝑠𝑒𝑙 𝑤𝑡. (%)) = 100 − 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑖𝑙𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (3)
PT

3.Analytical methods
CE

3.1.GC Analysis
AC

Biodiesel (FAME) produced from vegetable oils were analyzed using gas chromatography

(GC) AGILENT 6850 Series GC System. HP-1, with capillary column (DB-23 fused silica

Column - 202 × 200 × 105 mm (HWD)), Detector – Flame Ionization Detector, Split 1:50

and N2 Flow – 1 ml/min. Temperature programming in oven was maintained primarily at

160°C for 2 minutes at 6°C/min, 180°C for 2 minutes at 6°C/minutes and finally increased to

230°C for 10 minutes at 4°C/minute with injector and detector temperature maintained at 230

6
 ACCEPTED MANUSCRIPT

°C and 270°C. The standard was used Supelco 37 FAME mix (Sigma Aldrich) along with

samples.

3.2. Fuel property analysis

After each transesterification experiments, the biodiesel was analyzed for various fuel

characteristics such as density, kinematic viscosity, FLP, FRP, PP, CP (ASTM- D4052, D

PT
445, D 93, D 92, D97, D2500) was measured for all biodiesel as per the standard methods of

RI
biodiesel.

SC
3.3. DSC Thermograms NU
The thermograms of the resulted biodiesel was analyzed using differential scanning

calorimetry (DSC Q200 V24. 10 Build 122) (Pérez et al., 2010). Briefly, the samples were
MA

first heated to 100°C for 2 mins and then brought to 60°C and cooled at 1°C/min, 5°C /min

and 10°C /min. After comparing the various heating rates, 5°C/min was selected for this
D

study experiment. TCO (maximum temperature for crystallization Onset) was located from the
E

transition in the graph plotting Temperature (°C) and Heat Flow (mW) gives the exact
PT

temperature at which the biodiesel sample starts to have a transition from liquid to solid.
CE

4. Results & discussion

AC

The physicochemical characteristics of vegetable oil and biodiesel synthesized are shown in

Table 1 and Table 2. Undoubtfully, transesterification process resulted in maximum yield of

biodiesel from various vegetable oils, especially for jatropha and coconut oil resulting in

96.5% yield compared to other sources of biodiesel. The fact that the byproduct of glycerol

accumulation in from transesterification process might have resulted in not obtaining 100%

yield. Moreover, high viscosity diesel enables larger droplets upon injection that results in

7
 ACCEPTED MANUSCRIPT

poor combustion and increased emissions (Knothe & Dunn, 2009). It can be noted from

Table 1, oil from mahua, neem, rice bran and jatropha exhibited higher densities varied from

920-925 Kgm-3 compared to other vegetable oils. However, the density was found to lower in

the synthesized biodiesel which is due to the transesterification process and is consistent with

literature report (Esteban et al., 2012). Similarly, the viscosity was higher in neem, jatropha

and mahua resulted in 45.8 mm2s-1, 44.3 mm2s-1 and 41.6 mm2s-1. However, the density and

PT
viscosity values were decreased upon transesterification process and are shown in Table 2. It

RI
can be observed that the viscosity of the vegetable oil is approximately 10-20 fold lesser than

SC
that of the synthesized biodiesel and is well in agreement with the reported literature (Nabi et

al., 2009).The density and the viscosity of the biodiesel obtained from jatropha oil is very
NU
high with 888 kg m-3 and 5.6 mm-2s-1 compared to another biodiesel. Furthermore, the density

and the viscosity of the values are within the limits prescribed EN14214:2003 and
MA

IS15607:2005 well accepted biodiesel standards. Flash point is lowermost temperature at

which the biodiesel will ignite with absence of vapor at a rate to sustain the fire. The fire
D

point of biodiesel may be defined as the temperature at which aids in burning for at least 5
E

seconds’ post ignition by an open flame. For all biodiesel, the flash point was within the
PT

range of 152 °C – 182°C and fire point between the range of 175 °C – 195 °C which is higher
CE

when compared to the EN1414:2003 and IS15607:2005 standard. This indicates that all

biodiesel has a higher flash point and fire point they are safe for handling and transportation
AC

(Gumus, 2010). Similarly, the composition of FAMEs from vegetable oil is shown in Table 3.

It can be noted that presence of unsaturated outlays the saturated fatty acid in all the biodiesel

obtained. The maximum percentage (%) of the total unsaturated fatty acid (C 18:1 and C18:2)

was found higher in sunflower oil, jatropha oil and neem oil in the range of 88.20%, 77.58%

and 73.92 respectively. Similarly, the maximum percentage (%) of total saturated fatty acid

was found higher in coconut oil, palm oil and mahua oil and were in the range of 58.87%,

8
 ACCEPTED MANUSCRIPT

40.68% and 38.65% respectively. This results follow the same trend of the saturated fatty

acid composition in literature reported (Liu, 2015). Furthermore, the melting temperature of

each saturated and unsaturated compound has a direct impact on the overall melting

temperature of the oil and biodiesel called as a eutectic mixture (Lee et al., 1995). From the

Table 4, it can be perceived that, sunflower oil, jatropha oil and mahua oil exhibited onset

crystallization temperature of -3.81°C, 1.20°C and 1.42°C respectively. This is due to higher

PT
existence of unsaturated fatty acid point can have the dominating impact on the overall

RI
melting temperature (Knothe & Dunn, 2009).

SC
The effect of various temperatures on liquid fraction yield of winterized biodiesel from

vegetable oil is shown in Table 5. During the winterization process, most of the high melting
NU
(FAMEs) separates out leading to formation of turbidity or precipitation. As pure biodiesel is
MA

preferred over biodiesel-diesel blends, to have better exhaust emissions, and to avoid addition

of the second substance such as fuel additives, the use of pure biodiesel after winterization is
D

the safer and easier option. Based on this study, it can be concluded that by winterizing
E

sunflower biodiesel up to 0°C as no solid fraction is obtained and can be used directly without
PT

any winterization up to 0°C. Similarly, coconut biodiesel resulted in 3.34 % of solid upon

winterization up to 5°C and hence can be used > 5°C. Similarly, jatropha and rice bran
CE

biodiesel can be winterized at 10°C with solid fraction removal of 3.5 %. Palm and Mahua
AC

biodiesel can be used only at temperatures above 15°C and the solid fraction removal was

about 0-6.24 %. Furthermore, neem biodiesel can be used only above 20°C. Based on our

initial screening process, we observed 5°C /min exhibited TG profile of the samples were

better. Yet, this profile varies with respect to samples as castor oil exhibited 10°C /min

compared to higher heating rates (Conceição et al., 2007). Tan & Man (2002) showed that

low heating rate (5°C /min) favors for thermal equilibrium of vegetable oils when compared

to other heating rates indicating our observation is very consistent. Further, the DSC cooling
9
 ACCEPTED MANUSCRIPT

thermograms were obtained at the proportion of 5°C /min and are shown in Figure 2 for

various biodiesel. The biodiesel from coconut oil and palm oil exhibited four melting points

of 3.59°C, - 2.21°C, - 8.47°C, – 14.27°C and 13.48°C, 10.41°C, 7.22°C and –33.38°C

respectively. Similarly, biodiesel from neem oil, rice bran oil and mahua oil resulted in three

melting points of 8.89°C, 5.8°C and 3.06°C; 1.20°C, - 4.15°C and – 14.27°C, 7.78°C, 5.01°C

and 3.55°C respectively. Furthermore, the biodiesel from sunflower biodiesel showed two

PT
melting temperatures at 1.42°C and – 6.99°C and the biodiesel from jatropha oil showed only

RI
one temperature of -3.81°C. The Rice bran oil showed two distinct peaks which may be due

SC
to the equal distribution of linoleic and oleic acid content are in consistent with the literature

(Ajithkumar et al., 2009). Interestingly, these disparities in different melting point amongst
NU
vegetable oil are due to the presence of the mixed unsaturated and saturated fatty acids in the

biodiesel (Dunn, 1999). Comparing the above results, we find the order of increasing
MA

crystallization temperature for different vegetable oil biodiesel were jatropha> sunflower>

rice bran> coconut> mahua> neem > palm.

E D

5.Conclusions
PT

Biodiesel was produced from seven different vegetable oils – sunflower, coconut, rice bran,
CE

palm, jatropha, mahua and neem oil by acid or alkali transesterification process. The yield by

transesterification was 92 – 97 % and coconut oil yield higher quantity of biodiesel. Different
AC

fuel properties were measured for all the biodiesel and they meet biodiesel specifications. The

GC analysis shows that all the oils vary significantly in their fatty acid compositions. Based

on winterization studies, jatropha biodiesel exhibits no solid fraction is obtained up to 0oC

and can be a promising biodiesel. Similarly, the coconut biodiesel resulted solid fraction upon

winterization up to 5°C followed by jatropha and rice bran biodiesel at 10°C. The palm and

mahua biodiesel can be used only at temperatures above 15°C. Since, neem biodiesel

10
 ACCEPTED MANUSCRIPT

possesses poor cold flow properties and it can be used only above 20°C because solid fraction

formation at 15°C is nearly 38.5 %.

Acknowledgement

PT
We thank Dr. Gildhyal, ONGC, Chennai for helping us in fuel properties analysis.

RI
References

SC
Ajithkumar, G., Jayadas, N.H. and Bhasi, M., 2009. Analysis of the pour point of coconut

oil as a lubricant base stock using differential scanning calorimetry. Lub. Sci., 21, 13-26.
NU
Bhale, P.V., Deshpande, N.V., Thombre, S.B. 2009. Improving the low temperature
MA

properties of biodiesel fuel. Renew. Energ., 34, 794-800.

Canoira, L., Alcantara, R., García-Martínez, M.J., Carrasco, J. 2006. Biodiesel from
D

Jojoba oil-wax: Transesterification with methanol and properties as a fuel. Biomass

E

Bioenergy, 30, 76-81.

PT

Cao, L., Wang, J., Liu, C., Chen, Y., Liu, K., Han, S. 2014. Ethylene vinyl acetate

copolymer: A bio-based cold flow improver for waste cooking oil derived biodiesel
CE

blends. Appl. Energ., 132, 163-167.

AC

Chastek, T.Q. 2011. Improving cold flow properties of canola-based biodiesel. Biomass

Bioenergy, 35, 600-607.

Cheong, Y.-W., Min, J.-S., Kwon, K.-S. 1998. Metal removal efficiencies of substrates

for treating acid mine drainage of the Dalsung mine, South Korea. J. Geochem. Exp., 64,

147-152.

11
 ACCEPTED MANUSCRIPT

Conceição, M.M., Candeia, R.A., Silva, F.C., Bezerra, A.F., Fernandes Jr, V.J. and

Souza, A.G., 2007. Thermoanalytical characterization of castor oil biodiesel. Renew.

Sust. Energ. Rev.,, 11, 964-975.

Demirbas, A. 2007. Progress and recent trends in biofuels. Prog. Energ. Comb. Sci. 33, 1-

18.

Doğan, T.H., Temur, H. 2013. Effect of fractional winterization of beef tallow biodiesel

PT
on the cold flow properties and viscosity. Fuel, 108, 793-796.

RI
Dunn, R.O. 1999. Thermal analysis of alternative diesel fuels from vegetable oils. J.

SC
Amer. Oil. Chemist. Soc., 76, 109-115.

Esteban, B., Riba, J.-R., Baquero, G., Rius, A., Puig, R. 2012. Temperature dependence
NU
of density and viscosity of vegetable oils. Biomass Bioenergy, 42, 164-171.

EN14214(2003).Automotive fuels-Fatty acid methyl esters (FAME) for diesel engine-

MA

Requirments and test methods.

Gómez, M.G., Howard-Hildige, R., Leahy, J., Rice, B. 2002. Winterisation of waste
D

cooking oil methyl ester to improve cold temperature fuel properties. Fuel, 81, 33-39.
E

Graboski, M., McCormick, R., Alleman, T., Herring, A. 2003. The effect of biodiesel
PT

composition on engine emissions from a DDC series 60 diesel engine. National

CE

Renewable Energy Laboratory (Report No: NREL/SR-510-31461).

Gumus, M. 2010. A comprehensive experimental investigation of combustion and heat

AC

release characteristics of a biodiesel (hazelnut kernel oil methyl ester) fueled direct

injection compression ignition engine. Fuel, 89, 2802-2814.

IS 15607 (2005). Bio-diesel (B 100) blend stock for diesel fuel (PCD 3: Petroleum,

Lubricants and their Related Products). https://archive.org/s tream/ gov.in.is. 15607.

2005/ is. 15607.2005_djvu. Accessed 13 Feb 2018.

12
 ACCEPTED MANUSCRIPT

Joshi, H., Moser, B.R., Toler, J., Smith, W.F., Walker, T. 2011. Ethyl levulinate: A

potential bio-based diluent for biodiesel which improves cold flow properties. Biomass

Bioenergy, 35, 3262-3266.

Karavalakis, G., Stournas, S., Bakeas, E. 2009. Light vehicle regulated and unregulated

emissions from different biodiesels. Sci. Tot. Environ., 407, 3338-3346.

Kerschbaum, S., Rinke, G., Schubert, K. 2008. Winterization of biodiesel by micro

PT
process engineering. Fuel, 87, 2590-2597.

RI
Knothe, G., Dunn, R.O. 2009. A comprehensive evaluation of the melting points of fatty

SC
acids and esters determined by differential scanning calorimetry. J. Amer. Oil. Chemist.

Soc., 86, 843-856.

NU
Kreulen, H. 1976. Fractionation and winterization of edible fats and oils. J. Amer. Oil.

Chemist. Soc., 53, 393-396.

MA

Kulkarni, M.G., Dalai, A.K. 2006. Waste cooking oil an economical source for biodiesel:

a review. Ind.Eng.Chem.Res., 45(9), 2901-2913

D

Lee, I., Johnson, L.A., Hammond, E.G. 1996. Reducing the crystallization temperature of
E

biodiesel by winterizing methyl soyate. J. Amer. Oil. Chemist. Soc., 73, 631-636.
PT

Lee, I., Johnson, L.A., Hammond, E.G. 1995. Use of branched-chain esters to reduce the
CE

crystallization temperature of biodiesel. J. Amer. Oil. Chemist. Soc., 72, 1155-1160.

Liu, G. 2015. Development of low‐temperature properties on biodiesel fuel: a review. Int.

AC

J. Energ. Res., 39, 1295-1310.

McCormick, R., Alleman, T., Waynick, J., Westbrook, S., Porter, S. 2006. Stability of

Biodiesel and biodiesel blends: Interim Report. National Renewable Energy Laboratory

(NREL), Golden, CO.

13
 ACCEPTED MANUSCRIPT

Moser, B.R., Vaughn, S.F. 2010. Evaluation of alkyl esters from Camelina sativa oil as

biodiesel and as blend components in ultra low-sulfur diesel fuel. Bioresour. Technol.,

101, 646-653.

Nabi, M.N., Rahman, M.M., Akhter, M.S. 2009. Biodiesel from cotton seed oil and its

effect on engine performance and exhaust emissions. Appl. Ther. Eng., 29, 2265-2270.

Nainwal, S., Sharma, N., Sharma, A.S., Jain, S., Jain, S. 2015. Cold flow properties

PT
improvement of Jatropha curcas biodiesel and waste cooking oil biodiesel using

RI
winterization and blending. Energy, 89, 702-707.

SC
Ooi, T., Teoh, C., Yeong, S., Mamot, S., Salmiah, A. 2005. Enhancement of cold stability

of palm oil methyl esters. J. Oil. Palm. Res., 17, 6.

NU
Pérez, Á., Casas, A., Fernández, C.M., Ramos, M.J., Rodríguez, L. 2010. Winterization

of peanut biodiesel to improve the cold flow properties. Bioresour. Technol., 101, 7375-
MA

7381.

Rasimoglu, N., Temur, H. 2014. Cold flow properties of biodiesel obtained from corn oil.
D

Energy, 68, 57-60.

E

Smith, P.C., Ngothai, Y., Nguyen, Q.D., O'Neill, B.K. 2010. Improving the low-
PT

temperature properties of biodiesel: Methods and consequences. Renew. Energ., 35,

CE

1145-1151.

Soriano, N.U., Migo, V.P., Matsumura, M. 2006. Ozonized vegetable oil as pour point
AC

depressant for neat biodiesel. Fuel, 85, 25-31.

Tan, C.P., Y. B. Man. Comparative differential scanning calorimetric analysis of

vegetable oils: I. Effects of heating rate variation. Phytochem. Anal., 13, 129-141.

Van Gerpen, J. 2005. Biodiesel processing and production. Fuel. Process. Technol., 86,

1097-1107.

14
 ACCEPTED MANUSCRIPT

Vedaraman, N., Puhan, S., Nagarajan, G., Velappan, K. 2011. Preparation of palm oil

biodiesel and effect of various additives on NOx emission reduction in B20: An

experimental study. Int. J. Green. Energ., 8, 383-397.

Wang, J., Cao, L., Han, S. 2014. Effect of polymeric cold flow improvers on flow

properties of biodiesel from waste cooking oil. Fuel, 117, 876-881.

Wang, Y., Ma, S., Zhao, M., Kuang, L., Nie, J., Riley, W.W. 2011. Improving the cold

PT
flow properties of biodiesel from waste cooking oil by surfactants and detergent

RI
fractionation. Fuel, 90, 1036-1040.

SC
NU
MA
E D
PT
CE
AC

Figure Captions

Figure 1. Transesterification reaction

15
 ACCEPTED MANUSCRIPT

Figure 2. DSC Cooling thermograms for various biodiesel

PT
RI
SC
NU
MA
E D
PT
CE
AC

16
 ACCEPTED MANUSCRIPT

Table 1. Vegetable oil - Physical Properties

Oil Sunflower Coconut Palm Rice Jatropha Mahua Neem

Bran

Density 918 919 910 921 920 925 922

(Kg/m3)

PT
Viscosity 28.3 30.6 32.7 33.2 44.3 41.6 45.8

At 40oC

RI
(mm2s-1)

SC
NU
MA
E D
PT
CE
AC

17
 ACCEPTED MANUSCRIPT

Table 2. Physicochemical Comparison of Biodiesel yield from different vegetable oil and

their fuel properties with standards

Biodiesel Yield % Density Viscosity Flash Fire Cloud Pour

(Kgm-3) at 40oC Point (oC) Point (oC) Point Point

(mm2s-1) (oC) (oC)

PT
Sunflower 94.2 % 866 2.6 169 193 -2 -6

Coconut 96.5 % 868 3.3 152 188 +4 -1

RI
Palm 95.4% 846 3.5 182 192 +10 +8

SC
Rice Bran 92.1 % 856 4.7 176 183 +4 0

Jatropha 96.5 % 888 5.6 170 176 +3 -6

NU
Mahua 92.7 % 881 5.3 174 185 + 12 4
MA

Neem 93.3 % 880 5.5 180 195 +12 +8

EN14214:2003 N.A 860-900 3.5-5 >120 - - -

IS15607:2005 N.A 860-900 2.5-6.0 120 - - -

E D

Diesel N.A 840-860 1.9-3.8 70 74 - -

PT
CE
AC

18
 ACCEPTED MANUSCRIPT

Table 3. Composition of vegetable oil fatty acid methyl ester and their corresponding melting point

Biodiesel C8:0 C10:0 C12:0 C14:0 C16:0 C18:0 C18:1 C18:2 C18:3 C20:0 C22:0 C24:0 Total Total

Sat.FA Unsat.FA

P T (%) (%)

Name Methyl Methyl Methyl Methyl Methyl Methyl Methyl Methyl Methyl Methyl

R I Methyl Methyl

of FAME

Melting
Caprylate

- 34
Caproate

- 18
Laurate

5
Myristate

18.5
Palmitate

30.55
Stearate

39.1
Oleate

- 20
Linoleate

- 35 -52
C
Linolenate

S
Arachidic

46.6
behenate

54
Lingnocerate

58 - -

Point

N U
of
A
FAME
M
(oC)

29]
[28,

E D
Sunflower - - - 0.071
P
6.288T 3.770 33.545 54.675 0.035 0.246 0.803 0.298 11.511 88.22

Coconut 0.424 1.301 22.018 15.179

C E 17.343 2.610 29.435 13.287 - - - - 58.875 42.722

Palm

Rice Bran
0.067

-
-

-
0.288

-
A C 0.749

0.527
36.766

19.515
-

2.953
46.482

38.109
13.745

34.297
0.524

0.638
0.123

1.984
0.072

-
0.063

-
38.652

25.617
60.227

72.406

Jatropha - - - 0.178 13.297 7.082 41.787 35.801 0.341 0.275 - - 21.173 77.588

Mahua - - - 1.045 17.838 21.798 48.016 9.276 - - - - 40.681 57.292

19
 ACCEPTED MANUSCRIPT

Neem - - - 2.387 12.913 11.396 35.492 38.435 - - - 0.348 27.044 73.927

P T
R I
S C
N U
A
M
E D
P T
C E
A C

20
 ACCEPTED MANUSCRIPT

Table 4. Crystallization Onset Temperature from DSC for different biodiesel

Biodiesel Sunflower Coconut Palm Rice Jatropha Mahua Neem

PT
Bran

RI
Crystallization 1.42 3.59 13.48 1.20 -3.81 7.78 8.89

SC
Onset (oC)
NU
MA
E D
PT
CE
AC

21
 ACCEPTED MANUSCRIPT

Table 5. Amount of liquid fraction in winterized biodiesel at different temperature

Biodiesel Liquid Fraction %

Temperature 0C Sunflower Coconut Mahua Rice Bran Palm Jatropha Neem

PT
20 100 100 100 100 100 100 100

RI
15 100 100 100 100 93.76 99.64 61.54

10 100 100 62.75 96.5 12.61 97.73 19.76

SC
5 100 96.66 NU0 34.48 0 81.82 0

0 100 64.88 0 0 0 77.41 0

MA
E D
PT
CE
AC

22
 ACCEPTED MANUSCRIPT

Highlights

 Biodiesel was prepared using seven different vegetable oil.

 Temperature effect on winterization of biodiesel was investigated

 DSC was used to estimate the crystallization onset temperature

 Sunflower biodiesel recorded no crystal formation with minimum temperature of 0ºC.

PT
.

RI
SC
NU
MA
E D
PT
CE
AC

23
Figure 1
Figure 2r1
Figure 2r2