b i o m a s s a n d b i o e n e r g y 3 4 ( 2 0 1 0 ) 1 3 0 9 e1 3 1 3

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Effect of cold flow improvers on flow properties

of soybean biodiesel

Chen Boshui*, Sun Yuqiu, Fang Jianhua, Wang Jiu, Wu Jiang

Dept. of Petrochemistry, Logistical Engineering University, University Town, Shapingba District, Chongqing 401311, PR China

article info abstract

Article history: The influence of three cold flow improvers, namely, olefin-ester copolymers (OECP),
Received 29 July 2008 ethylene vinyl acetate copolymer (EACP) and polymethyl acrylate (PMA), on the low-
Received in revised form temperature properties and viscosityetemperature characteristics of a soybean biodiesel
22 March 2010 was evaluated on a low-temperature flow tester and a rotatory rheometer. The crystal
Accepted 6 April 2010 morphologies of the biodiesel at low temperatures were investigated through a polarizing
microscope. The results indicated that the ability of the cold flow improvers differed in
Keywords: improving the cold flow properties of soybean biodiesel, of which OECP was the best
Biodiesel candidate. OECP can significantly reduce pour point (PP) and cold filter plugging point
Cold flow improvers (CFPP) of biodiesel and retard viscosity increase of biodiesel at low temperatures when
Pour point incorporated into biodiesel at the additive contents of 0.03%. On the other hand, OECP
Cold filter plugging point functioned by inhibiting the wax crystals from growing to a larger size and provided
Viscosity a barrier to crystal agglomeration at low temperatures, thus improving the cold flow
properties of soybean biodiesel.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
In the last decades, the awareness of energetic and environ-
mental problems encouraged many researchers to explore the
possibility of using alternative fuels instead of petroleum and
its derivatives. Biodiesel, derived from renewable vegetable
oils or animal fats with a process of transesterification and
commonly referred to as fatty acid methyl esters (FAME), has
proven itself as an prominent candidate for petroleum diesel
fuel. Since the beginning of the 1990s, a considerable interest
has been taken in developing biodiesel [1e5]. Virtually, bio-
diesel is technically competitive with conventional petroleum
diesel fuel and offers a number of advantages over petroleum
fuels, such as enhanced biodegradability, reduced toxicity,
lower emissions and increased lubricity [6]. Although the
above attributes of biodiesel have drawn attention to this
renewable resource as a substitute of petroleum fuel, there
exist some significant drawbacks that have limited its appli-
cation. One of the major problems associated with the use of
biodiesel as the diet of diesel engines is poor low-temperature
flow property. It has been found that crystallization or thick-
ening of biodiesel at low temperatures causes fuel starvation
and operability problems as solidified materials clog fuel lines
and filters, mainly due to its high amount of saturated FAME
components [7,8]. In recent years, several approaches to the
low-temperature problems of biodiesel have been investi-
gated including blending with conventional diesel fuels,
winterization, additives, branched-chain esters, amongst
which treatment with chemical additives seems to be the
most convenient and economical, and thereby the most
attractive [9e13]. Although some additives have so far been
reported to be effective in improving the cold flow property of
biodiesel [14e16], improvement of the low-temperature flow
characteristics of biodiesel by the addition of additives still

* Corresponding author. Tel.: 86 23 86730832.

E-mail address: chenboshui@yahoo.com.cn (C. Boshui).
0961-9534/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.04.001
1310 b i o m a s s a n d b i o e n e r g y 3 4 ( 2 0 1 0 ) 1 3 0 9 e1 3 1 3
Table 1 e Typical specifications for the cold flow
improvers.
Item OECP EACP PMA
Appearances Light yellow Brownish Light yellow
viscous yellow oily viscous
Density (20  C, g cm3) 0.886 0.853 0.878
Freezing point ( C) 5 7 3
Kinematic viscosity 18.64 15.58 17.45
(100  C, mm2 s1)
remains a challenge and needs further investigation. The
present work deals with the influence of some polymeric cold
flow improvers on the cold flow properties of soybean-based
biodiesel.
2. Materials and methods
2.1. Soybean oil
As a biodiesel origin, the soybean oil used for the production of
the FAME in the present study was a bland, greenish-yellow,
bright and clear oily liquid obtained from Chongqing Grain
and Oil Corporation, China. It has been well processed
(hydration- and phosphoric acid-degummed, caustic-
neutralized, water-washed, bleached and deodorized) to
remove undesirable substances such as free fatty acids,
phosphatides, color bodies, sterols, ketones, and peroxides,
with the appropriate color for cooking and baking applica-
tions. Chromatographic analysis has shown that the major
unsaturated fatty acids in the soybean oil are 6.9% alpha-
linolenic acid (C-18:3), 55.4% linoleic acid (C-18:2), and 23.4%
oleic acid (C-18:1). The soybean oil also contains the saturated
fatty acids of 3.7% stearic acid and 10.6% palmitic acid.
2.2. Cold flow improvers
Three commercial diesel fuel cold flow improvers, namely,
HS-J015, KT1103 and XFT122, were selected for testing. Virtu-
ally, HS-J015 is chemically a mixture of olefin-ester copoly-
mers (OECP) provided by Huashen Hi-Tech Co. Ltd., Xian,
China. KT1103 is an ethylene vinyl acetate copolymer (EACP)
provided by Kangtai Petrochemicals Co. Ltd., Shenyang,
China, while XFT122 is polymethyl acrylate (PMA) obtained
from Xiefeng Chemicals Co. Ltd., Nangjing, China. Shown in
Table 1 are typical specifications for the three cold flow
improvers. Prior to the testing, appropriate amount of the cold
flow improvers was incorporated into soybean biodiesel in the
mass percentages of 0.00%, 0.01%, 0.03% and 0.05%, respec-
tively. The formulated biodiesels were thoroughly mixed
under 60  C and were thereafter ready for testing.
2.3. Preparation of soybean biodiesel
Soybean biodiesel (SME) was prepared by reacting 700 g of
soybean oil, 151 g CH3OH and 7 g NaOH. The reaction was
carried out for 100 min under reflux at 60e65  C with agitation.
After reaction, the reaction mixture was allowed to stand
overnight and the methyl ester layer was separated from the
glycerol layer using a separatory funnel. Residual amount of
glycerol in the crude methyl ester was removed by centrifu-
gation. The methyl ester was purified by distilling-off the
unreacted methanol under atmospheric pressure, washing
several times with water, centrifugation and drying with
anhydrous Na2SO4.
2.4. Pour point and cold filter plugging point
measurements
Pour point (PP) and cold filter plugging point (CFPP) are
important indices related to low-temperature operability of
diesel fuels. The pour point is the temperature at which a fuel
can no longer be poured due to gel formation, while the cold
filter plugging point is the temperature at which a fuel jams
the filter due to the formation of agglomerates of crystals. In
the present test, PP and CFPP of the formulated soybean bio-
diesels were measured on a low-temperature flow tester
following the SH/T0248 procedures. (SH/T0248 is a Chinese
method for determining PP and CFPP. Determinations of PP
and CFPP by this method well correspond to ASTM D-97 and
EN 116, respectively).
2.5. Viscosity measurements
Diesel fuel viscosity not only affects atomization and density,
but also influences the cold flow property. In the present
investigation, dynamic viscosities of biodiesels at different
temperatures but the same shear rate were measured on
a VIARMES 95270 rotary rheometer (Sanchez Technologies,
France). Duplicate measurements were made for each sample
and the results were averaged.
2.6. Crystal morphology observation
Crystal morphologies of soybean biodiesel at low tempera-
tures were observed using a polarizing microscope modeled
DMLP (Leica, Germany). The microscope is equipped with
a cooling system and, prior to observation, biodiesel samples
were progressively cooled with liquid nitrogen from room
temperature at the rate of 2  C per minute. When biodiesel
began to gel at certain temperatures, the cooling rate was
slowed down and carefully controlled at 1  C per minute so as
to ensure plenary growth of wax crystals.
3. Results and discussion
3.1. Effect of additives on cold flow properties
The impacts of three cold flow improvers on the pour point
and cold filter plugging point of soybean biodiesels are listed
in Table 2.
From Table 2 it can be seen that the effects of OECP, EACP
and PMA on the cold flow properties of soybean biodiesel were
different, of which OECP was the most effective. With 8  C
decreases in the pour point and 6  C decreases in the cold filter
plugging point, OECP was very efficient in decreasing both PP
and CFPP of soybean biodiesel at the additive content of 0.03%,
 b i o m a s s a n d b i o e n e r g y 3 4 ( 2 0 1 0 ) 1 3 0 9 e1 3 1 3 1311

Table 2 e Effect of cold flow improvers on low-

temperature properties of soybean biodiesel.
Sample Additive content PP ( C) CFPP ( C)
(m, %)

SME 0.00 1 0
SME OECP 0.01 4 2
0.03 9 6
0.05 2 1
SME EACP 0.01 3 0
0.03 1 1
0.05 0 1
SME PMA 0.01 1 1
0.03 0 2
0.05 2 0

although at higher contents, e.g. 0.05%, it provided little effect

on PP and CFPP. Comparatively, EACP and PMA showed almost
no impact on the PP and CFPP of biodiesel at all additive
loadings tested, even though they have been proven to be
excellent pour point depressants for petrodiesels. Differences
in the impact of OECP, EACP and PMA on the cold flow prop-
erties of biodiesel may be attributed to their specific interac-
tions with wax crystals.
3.2. Viscosityetemperature relationship
The dynamic viscosities of the neat soybean biodiesel and the
biodiesels loaded with 0.03% of OECP, EACP and PMA,
respectively, at different temperatures are given in Table 3.
It can be seen from Table 3 that the viscosities of the bio-
diesels increased with decreasing temperature. It is also clear
that the viscosities of all biodiesels increased dramatically
below the temperature of about 0  C, which is just close to the
pour point or cold filter plugging point of the individual
bidiesel as shown in Table 2. Sharp increase in viscosity at the
temperatures below PP or CFPP may be an attribute of poor
cold flow properties for soybean biodiesel. However, the
increase of viscosity below PP or CFPP for biodiesels treated
with OECP, EACP and PMA was somewhat different. Below PP
and CFPP, the viscosities of biodiesels blended with OECP at
the temperatures tested were comparatively much smaller
than those of fuels loaded with EACP and PMA at the same
temperatures. This indicated that OECP was more excellent in
retarding viscosity increase of soybean biodiesel at low
temperatures than EACP and PMA, and the result was well
correlated with the fact that OECP provided better ability in
improving the low-temperature properties of soybean bio-
diesel as evidenced by PP and CFPP measurements shown in
Table 2.
Fig. 1 e Natural logarithm of dynamic viscosity versus
reciprocal Kelvin temperature for SMEs with and without
OECP.
The influence of temperature on the dynamic viscosities of
soybean biodiesels can further be described using the Arrhe-
nius equation:
h AeDEh =RT (1)
Taking the natural logarithm of the Arrhenius equation
yields:
DEh 1
ln h  ln A (2)
R T
where h is the dynamic viscosity (mPa s), A is pre-exponential
constant (mPa s), T the absolute temperature (K), R is the
universal gas constant (J mol1 K1) and DEh is the flow acti-
vation energy (J mol1). Shown in Fig. 1 are the natural loga-
rithms of dynamic viscosities of neat soybean biodiesel and
the biodiesel formulated with 0.03% of OECP as a function of
reciprocal Kelvin temperature in the temperature range of 20
to 50  C.
It is found from Fig. 1 that, for both neat biodiesel and the
formulated biodiesel, there are linear relations between the
viscositys logarithm and absolute temperatures reciprocal in
the temperature ranges of 0e50  C for neat biodiesel and of
10 to 50  C for the formulated biodiesel. (The lower limits of
the temperature ranges, i.e. 0  C and 10  C, are close to the PP
or CFPP of neat bidiesel and the formulated biodiesel,
respectively). This implied that at temperatures higher than

Table 3 e Dynamic viscosities of biodiesels at different temperatures.

Sample Dynamic viscosity (mPa$s)

50  C 40  C 30  C 20  C 10 0 C 5  C 10  C 15 C 20  C

SME 2.93 4.13 5.53 6.64 9.26 14.87 63.23 125.46 194.78 325.52
SME OECP 3.11 4.78 5.39 6.85 10.83 14.66 18.57 28.25 116.38 215.37
SME EACP 3.08 4.23 5.45 6.52 9.66 13.93 51.68 84.51 183.27 258.57
SME PMA 3.15 4.11 5.68 6.32 10.26 15.13 45.65 80.17 170.38 272.44
1312 b i o m a s s a n d b i o e n e r g y 3 4 ( 2 0 1 0 ) 1 3 0 9 e1 3 1 3
Fig. 2 e Polariscopic images of crystal morphologies of soybean biodiesel with/without OECP.
PP or CFPP, the soybean biodiesels exhibited Newtonian
behavior. Furthermore, dramatic increase in dynamic viscos-
ities of the biodiesels at the temperatures below PP or CFPP
can be more clearly observed. Nonlinear relations between the
viscositys logarithm and absolute temperatures reciprocal
indicated that the biodiesels became non-Newtonians at the
temperatures lower than PP or CFPP.
3.3. Crystal morphology
Shown in Fig. 2 are polarizing microscopic images of crystal
morphologies of neat soybean biodiesel and soybean biodiesel
treated with 0.03% OECP at 10  C and 20  C, respectively.
It is known that in polarizing microscopic analysis, crystal
substances well reflect polarized light and can therefore be
observed clearly exhibiting white images, while amorphous
substances do contrarily and exhibit black images. Therefore
from Fig. 2 we can see that the amount, shape and size of
crystals produced by neat biodiesel and the formulated bio-
diesel at low temperatures are quite different. For neat bio-
diesel, large amount and big size of wax crystals can be
observed and the crystals rapidly grew and agglomerated as
temperature decreased from 10  C to 20  C (Fig. 2a and b).
As to biodiesel with OECP, little crystal can be observed at
10  C although at lower temperatures such as 20  C, higher
amount of observable tiny regular-shaped wax crystals were
formed (Fig. 2c and d). It can naturally be inferred from the
polarizing microscopic analysis that OECP functioned by
reducing the size and amount and altering the shape of the
wax crystals of biodiesel. That is, it inhibited the crystals from
growing to a larger size and provided a barrier to crystal
agglomeration at low temperatures, thus extending the range
of fluidity of the biodiesel to lower temperatures.
4. Conclusions
From above investigations the following conclusions can be
drawn:
(1) The pour point and cold filter plugging point of neat
soybean biodiesel can be significantly reduced by formu-
lating appropriate amount, e.g., 0.03%, of a mixture of
olefin-ester copolymers (OECP) as a pour point depressant.
Other additives such as ethylene vinyl acetate copolymer
(EACP) and polymethyl acrylate (PMA) provided almost no
impact on the cold flow properties of soybean biodiesel.
(2) Dynamic viscosities of biodiesels increased dramatically
with decreasing temperature below pour points or cold
filter plugging points. However, the viscosity increase of
 b i o m a s s a n d b i o e n e r g y 3 4 ( 2 0 1 0 ) 1 3 0 9 e1 3 1 3
biodiesels at the temperatures below PPs or CFPPs can be
retarded by the addition of OECP.
(3) The action mechanisms for OECP to improve the cold flow
properties of soybean biodiesel can be ascribed on one
hand to the reduction of viscosity increase and on the
other hand to the inhibition of wax crystals from growing
and agglomerating to a larger size at low temperatures.
Acknowledgement
The authors gratefully acknowledge the financial support
from the Natural Science Foundation of Chongqing (project
no.: CSTC2006BA6031) and the Program for New Century
Excellent Talents in Chinese Universities (project no.: NCET-
04-1002). Special thanks go to Dr. Lun Zengmin of Petro-
chemical Research Institute, SINOPEC, for his technical
support with the viscosity measurements.
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Dr. Chen Boshui is a professor of Logistical Engineering Univer-
sity. His research interests mainly include biofuels and lubricating
materials. He has authored and co-authored more than 150
research and technical papers. He can be reached at phone: 86 23
86730832; e-mail: chenboshui@yahoo.com.cn; or postal address:
Department of Petrochemistry, Logistical Engineering University,
University town, Shapingba district, Chongqing 401311, PR China.