You are on page 1of 6

Biotechnology and Bioprocess Engineering 2008, 13: 505-510

DOI/10.1007/s12257-008-0144-y





Estimating and Improving Cold Filter
Plugging Points by Blending Biodiesels with
Different Fatty Acid Contents

dïáJq~Éâ gÉçåÖ
NIOæ
I g~ÉJeÉÉ m~êâ
OIPæ
I pÉçâJeï~å m~êâ
OIP
I ~åÇ açåJeÉÉ m~êâ
NIPIQIRISIT
G
1
School of Biological Sciences and Technology, Chonnam National University, Gwangju 500-757, Korea
2
Engineering Research Institute, Chonnam National University, Gwangju 500-757, Korea
3
Interdisciplinary Program of Graduate School for Bioenergy and Biomaterials, Chonnam National University,
Gwangju 500-757, Korea
4
Biotechnology Research Institute, Chonnam National University, Gwangju 500-757, Korea
5
Institute of Bioindustrial Technology, Chonnam National University, Gwangju 500-757, Korea
6
Research Institute for Catalysis, Chonnam National University, Gwangju 500-757, Korea
7
Functional Food Research Center, Chonnam National University, Gwangju 500-757, Korea


Abstract Biodiesels are alkyl esters produced by transesterification of higher fatty acids (aliphatic chains composed of 14 to 22
carbon units) from animal fats and/or vegetable oils. The cold filter plugging points (CFPP) of biodiesels are not only
higher than that of petro-diesel, but they also differ from the melting point of the raw (unesterified) materials. In this
study, we empirically derived equations that estimated the CFPP of a biodiesel based on its fatty acid content, using
various biodiesel blends containing four methyl esters with different fatty acid compositions: soybean (SME), palm
(PME), rapeseed (RME), and lard (LME). These blending ratio experiments yielded three equations that described the
correlation between CFPP and fatty acid content: Y (CFPP, °C) = −3.1X (blending ratio) − 12.7 (PME/SME); Y = 2.2X
− 10.7 (LME/SME); and Y = −4.0X − 13.0 (PME/RME). We also obtained the correlation between CFPP and total
saturated fatty acid methyl ester content in the biodiesels: Y (CFPP, °C) = 0.449X (total saturated fatty acid methyl es-
ter content, wt%) − 9.198. These empirical equations accurately predicted CFPP values of biodiesel compounds with
known fatty acid compositions, facilitating the use of diverse biodiesels in industrial fields. © KSBB

Keywords: biodiesel, transesterification, cold filter plugging point, prediction




INTRODUCTION

Over the past three decades, a substantial quantity of re-
search has focused on developing a novel renewable and
sustainable energy resource, in order to reduce greenhouse
gas emissions and substitute for non-renewable resources [1-
3]. Since biodiesels exhibit several properties that are com-
parable to those of petro-diesel, most notably cetane number,
flash point, and volumetric heating value, they may eventu-
ally be applicable as a petro-diesel and chemical substitute
[4-6]. Biodiesel is generally manufactured by acid-, alkali-,
and enzyme-catalyzed, or supercritical non-catalyzed, trans-

*Corresponding author
Tel: +82-62-530-1841 Fax: +82-62-530-1910
e-mail: dhpark@chonnam.ac.kr


The first two authors equally contributed to this work.
esterification processes [2,4,5,7,8].
Although biodiesel has gained importance as an environ-
mentally friendly and renewable fuel, it is still not cost-
effective. The cost of the raw materials comprises approxi-
mately 60~75% of total biodiesel production costs [5,9], and
material costs are sharply increasing with the increase in the
price of crude oil. The feedstocks employed in biodiesel pro-
duction are generally classified into edible- and non-edible
vegetable oils, animal fats, and waste oils [1,4,10,11].
The major limitation of a biodiesel derived from raw ma-
terials is its tendency to crystallize or gel at or below a spe-
cific low temperature, which can plug an engine filter [12].
This so-called “cold filter plugging point” (CFPP) is derived
from the low-temperature flow properties and the fatty acid
composition of a given biodiesel. High saturated fatty acid
levels yield higher CFPP values, because unsaturated fatty
compounds have lower melting points than the saturated
fatty compounds. Generally, biodiesels are graded as “sum
506

Table 1. Fatty acid methyl ester composition of the starting bio-
diesels, produced from used oils and fat
Fatty acid content (wt%)
Vegetable
oils and
animal fat

Palmitic
acid
(C16:0)
Stearic
acid
(C18:0)
Oleic
acid
(C18:1)
Linoleic
acid
(C18:2)
Linolenic
acid
(C18:3)
SME 10.39 4.39 23.17 53.19 7.68
RME 5.39 1.90 56.00 23.96 12.32
PME 40.50 5.29 41.26 10.88 0.36
LME 26.52 12.19 44.85 12.59 1.55
SME: soybean methyl ester, RME: rapeseed methyl ester, PME: palm methyl
ester, LME: lard methyl ester.


mer grade” and “winter grade” based on their CFPP values
[4,12,13]. Researchers have investigated several approaches
to ameliorating the low-temperature problems of biodiesel,
including blending it with conventional petro-diesel, winter-
ization techniques, additives, and incorporating branched-
chain esters or bulky chain substituents [12,13].
We then derived equations that estimated the CFPP of a
given biodiesel using the fatty acid compositions of the raw
material. In addition, we investigated how the specific fatty
acid compositions in the blended biodiesels influenced their
CFPP.


MATERIALS AND METHODS

Materials

The refined and bleached rapeseed oil, soybean oil, palm
oil, and lard used for this study were all of commercial grade.
Table 1 provides their fatty acid composition. Fatty acid
methyl ester reference standards for palmitic, stearic, lino-
lenic, linoleic, oleic, and heptadecanoic methyl ester, all >
99% pure, were purchased from Sigma Chemical Co. Ltd.
(St. Louis, MO, USA). Methanol, potassium hydroxide, and
all other chemicals were of analytical grade.

Apparatus

The reactions were conducted in a 1-L four-necked re-
actor equipped with a reflux condenser, a thermometer,
and a sampling port. The reactor was heated in a constant-
temperature heating jacket controlled by a PID tempera-
ture controller, which was capable of controlling the tem-
perature to within ±0.2°C of the setting point. Mixing was
provided by an electrical motor with a propeller-type im-
peller.

Reaction Procedures for Fatty Acid Methyl Esters

Initially, the reactor was charged with 400 g of oils and/or
lard and heated to the setting temperature with agitation. A
specific quantity of catalyst was dissolved in the required
Table 2. Blending ratios used in CFPP enhancement experi-
ments
Blending ratio (−)
Biodiesel blending
8/2 6/4 5/5 4/6 2/8
PME/SME X
1
X
2
X
3
X
4
X
5

LME/SME Y
1
Y
2
Y
3
Y
4
Y
5

PME/RME Z
1
Z
2
Z
3
Z
4
Z
5

PME: palm methyl ester, SME: soybean methyl ester, LME: lard methyl ester,
RME: rapeseed methyl ester.


amount of methanol and also heated. After both reactant and
catalyst achieved the setting temperature, the methanolic
catalyst was introduced to the base of the reactor to prevent
methanol evaporation. The reaction was timed immediately
after the addition of catalyst and methanol. The reaction
experiment parameters were as follows: oil-to-methanol
molar ratio of 1:6, potassium hydroxide of 1% (w/w),
reaction temperature of 65°C, agitation speed of 2,000 rpm,
and reaction time of 20 min [2,11].

Experimental Design

In order to investigate changes in CFPP with respect to
fatty acid composition, rapeseed, soybean, palm, and lard
biodiesels were blended at different percent weight ratios, as
follows: 20:80, 40:60, 50:50, 60:40, and 80:20. In this way,
15 biodiesel samples were prepared and used for experi-
ments, as shown in Table 2.

Analytical Methods

nì~åíáí~íáîÉ ^å~äóëáë çÑ c~ííó ^ÅáÇ jÉíÜóä bëíÉê
`çåíÉåí
Fatty acid methyl ester contents were measured with KS
H ISO 5508 (Animal and vegetable fats and oils analysis by
gas chromatography of methyl esters of fatty acids) [14].
The analyses were conducted on a gas chromatograph
(Donam Instruments Inc., Korea) using a fused silica capil-
lary column (HP-INNOWAX, Agilent Technologies, USA)
and a flame-ionization detector with an injector temperature
of 250°C, an oven temperature of 210°C, and a detector
temperature of 250°C.

^ÅáÇ s~äìÉ
Acid values were assessed with KS M ISO 6618 (Petro-
leum products and lubricant determination of acid or base
number: colour indicator titration method) [15].

fçÇáåÉ kìãÄÉê
Iodine numbers were subsequently measured with the
Wijs titration method. Wijs titration was conducted as fol-
lows: samples were dissolved in 1.0 mL cyclohexane and
mixed with iodine monochloride (Wijs solution), after which
a cork was inserted and the solution was allowed to stand for
30 min. Subsequently, 2 mL potassium iodide and 10 mL
Biotechnol. Bioprocess Eng. 507

Table 3. Quality characteristics of the starting biodiesels, pro-
duced from used oils and fat
Properties SME RME PME LME Analysis method
Acid value
(mg KOH/g)
Iodine number
Viscosity
(40°C, mm
2
/s)
CFPP (°C)
0.17

131
4.11

−3
0.12

103
3.72

−6
0.26

51
4.07

9
0.22

68
3.95

8
KS M ISO 6618

Wijs test
Viscometer

CFPP tester


water were added, and the prepared sample solutions were
titrated using 0.1 mol/L thiosulfate [16].

sáëÅçëáíó
Viscosity was assessed with a viscometer (DV-II+Pro,
Brookfield Engineering Laboratories, Inc., MA, USA) at
40°C and 150 rpm.

`çäÇ cáäíÉê mäìÖÖáåÖ mçáåí E`cmmF
CFPP was measured using an automatic CFPP tester (Ta-
naka AFP-102, Cannon Instrument Company, Japan), as
follows: about 45 mL sample was cooled at 1°C increments,
while a 200-mm H
2
O vacuum was applied to draw the sam-
ple up into a pipette through a cold filter. The temperature at
which the sample failed to flow through the filter within 60
sec, or failed to return into the test jar, was recorded as the
CFPP.


RESULTS AND DISCUSSION

Analyses of Biodiesel Samples from Several Oils and
Fat

Because of their fatty acid compositions, palm oil and
animal fats have certain disadvantages with regard to diesel
engine applications. Biodiesels derived from animal fats,
which have higher levels of saturated fatty acids, exhibit
undesirable properties at colder temperatures that can pose
some problems in wintertime operation. On the other hand,
the high degree of fatty acid saturation inherent to these bio-
diesels enhances other fuel properties that are quite desirable
in a fuel source; specifically, heating value and cetane num-
ber [1,4,17].
Quality data on the four biodiesel samples are presented in
Tables 1 and 3. The fatty acid methyl ester contents of the
four biodiesel samples were within the limitations specified
by Korean regulatory agencies (over 96.5 wt%). The methyl
esters exhibited the following fatty acid contents: soybean
biodiesel, 99.4%; rapeseed biodiesel, 97.9%; palm biodiesel,
98.7%; and lard biodiesel, 97.8%. The specific fatty acid
compositions of the biodiesel samples are provided in Table
1. These results agree with previous work on biodiesel prop-
erties [12].
The soybean biodiesel consisted mostly of linoleic and
oleic acids, with an unsaturated fatty acid content of over
15%. Rapeseed biodiesel contained a large amount of oleic

















Fig. 1. Relationship between the empirical CFPP and saturated
fatty acid contents of four blended biodiesels.


acid, and its unsaturated fatty acid content was over 92%.
Palm biodiesel was largely composed of palmitic and oleic
acids, with an unsaturated fatty acid content of nearly 54%.
Lard biodiesel consisted mostly of oleic acids and palmitic
acid, and the unsaturated fatty acid content was nearly 61%.
The soybean, rapeseed, palm, and lard biodiesels exhibited
respective saturated fatty acid contents of 14.8, 7.3, 45.8, and
38.7%, and they exhibited CFPP values of −3, −6, 9, and
8°C, respectively. Knothe [13] also reported that saturated
fatty acid compounds had significantly higher melting points
than unsaturated fatty acid compounds, and Park et al. [12]
reported that to satisfy mandatory CFPP requirements, rape-
seed biodiesel was desirable because of its exceptionally
high oleic acid levels. The acid values ranged between 0.12
and 0.26 mg KOH/g, and the viscosities for soybean, rape-
seed, palm, and lard biodiesels were 4.11, 3.72, 4.07, and
3.95 mm
2
/s, respectively (Table 3).

Relationship between Saturated Fatty Acid Methyl
Ester Content and CFPP

Biodiesels produced from vegetable oils and animal fats
exhibit low-temperature related properties that are not as
prevalent in petroleum diesel, because the saturated fatty
acids in biodiesel are mainly palmitic and stearic acids. Fig.
1 shows the relationship between the saturated fatty acid
methyl ester content in the biodiesels and their CFPP values.
Saturated fatty acid levels linearly correlated with the CFPP.
Among the oils and fat we studied, rapeseed biodiesel con-
tained the lowest levels of saturated fatty acid (7.29 wt%),
and consequently the lowest CFPP (−6°C).

Effect of Blending Ratio on CFPP

Traditionally, vegetable oils and their derivatives are
“winterized”, blended together to facilitate handling and
pouring at colder temperatures. Based on this principle,
508

A














B















C














Fig. 2. Relationship between the CFPP with respect to the
blending ratio of the biodiesels. (A) Soybean biodiesel
(SME)/palm biodiesel (PME), (B) soybean biodiesel
(SME)/lard biodiesel (LME), and (C) rapeseed biodiesel
(RME)/palm biodiesel (PME).


blending biodiesels with different fatty acid compositions
should improve the cold temperature flow properties of bio-
diesel. For example, when palm and rapeseed biodiesels are
blended, the blended biodiesel will have a lower CFPP than
palm biodiesel [12].
In order to determine whether biodiesel could impart its
desirable low temperature properties to a blended biodiesel
containing other constituents, we prepared blended samples
containing soybean, rapeseed, palm, and lard biodiesels
manufactured from several origins (Table 2). Specifically,
we blended the lard or palm biodiesels, which contained
high levels of saturated fatty acids, with soybean or rapeseed
biodiesels, which contained low saturated fatty acid levels.
As a result, increasing the high-unsaturated to high-saturated
blending ratio decreased the CFPP of the mixture (Fig. 2).
When we blended palm biodiesel with soybean biodiesel
in the range of 20~80 (wt%), the CFPP of the blended bio-
diesels decreased linearly as the weight percent of the soy-
bean biodiesel increased (Fig. 2A), indicating that supple-
menting in the low-CFPP soybean biodiesel lowered the
high CFPP of the palm biodiesel. When soybean biodiesel
comprised more than 80 wt% of the blended biodiesel, the
CFPP dropped below 0°C. These results may be due to en-
richment with linoleic and oleic acids from the soybean bio-
diesel.
The correlation between the CFPP and the blending ratio
of the biodiesels from Fig. 2A can be expressed mathemati-
cally as follows: Y = −3.1X + 12.7 (Eq. 1), where X is the
blending ratio of palm biodiesel to soybean biodiesel, and Y
is the CFPP (°C). The regression coefficient (R
2
) was 0.989.
Therefore, when the blending ratios of palm/soybean bio-
diesels are known, the CFPP can be predicted by using Eq. 1.
Blending the palm and soybean biodiesels in increasing
amounts sharply decreased the saturated fatty acid content
(data not shown).
When we blended lard biodiesel with soybean biodiesel in
the range of 20~80 (wt%), the CFPP of the blended bio-
diesels decreased with the weight percent of soybean bio-
diesel (Fig. 2B). As before, adding the low-CFPP soybean
biodiesel lowered the high CFPP of lard biodiesel, and when
the blend consisted of more than 80% soybean biodiesel, the
CFPP of the blended biodiesel dropped to 3°C. This result
demonstrated that blending lard biodiesel with soybean bio-
diesel did not sufficiently control the CFPP, possibly be-
cause the lard contained 26.5% palmitic acid but only 12.2%
stearic acid. Based on these findings, we surmised that be-
tween these two saturated fatty acids, stearic acid might be
more sensitive to the CFPP change than palmitic acid. The
correlation between the CFPP and the blending ratio of the
biodiesels from Fig. 2B was as follows: Y = −0.06X + 7.6
(Eq. 2), where X is the blending ratio of lard biodiesel and
soybean biodiesel and Y is the CFPP (°C). The regression
coefficient (R
2
) was 0.985. When the blending ratio of a
lard/soybean biodiesel is known, its CFPP can be predicted
using Eq. 2.
When palm biodiesel was blended with rapeseed biodiesel
in the range of 20~80 (wt%), the CFPP of the blended bio-
diesels decreased with the weight percent of rapeseed bio-
diesel (Fig. 2C), indicating that, like soybean, the lower
CFPP of the rapeseed biodiesel lowered the high CFPP of
the palm biodiesel. In this case, however, when rapeseed
biodiesel was present at only 60 wt% or greater, the CFPP of
Biotechnol. Bioprocess Eng. 509

A
















B

















C















Fig. 3. Relationship between the CFPP of the blended bio-
diesels and the levels of palmitic acid (A), stearic acid (B),
and total saturated fatty acids (C).


the blended biodiesel dropped below 0°C. These results may
be the result of the unsaturated fatty acid content increase
from the rapeseed biodiesel, which is enriched in oleic and
linoleic acids (56 and 24%, respectively). The correlation
between the CFPP and the blending ratio of biodiesels ob-
tained from Fig. 2C as follows: Y = −4.0X + 13 (Eq. 3),
where X is the blending ratio of palm biodiesel and rapeseed
biodiesel and Y is the CFPP (°C). The regression coefficient
(R
2
) was 0.964. Therefore, when the blending ratio of a rape-
seed/palm biodiesel is known, the CFPP can be predicted
using Eq. 3.
Fig. 3 summarizes the CFPP values of all of the blended
biodiesels, based on their different fatty acid compositions.
Among the individual saturated fatty acids, palmitic acid
methyl ester content in biodiesels exhibited the best correla-
tion with CFPP (Fig. 3A), as represented mathematically by
the following equation: Y = 0.186X − 7.547 (Eq. 4), where
X is the palmitic acid methyl ester content of the biodiesel,
and Y is the CFPP (°C). The regression coefficient (R
2
) was
0.845. Therefore, one can utilize Eq. 4 to estimate the CFPP
of a biodiesel, if its palmitic acid methyl ester content is
known.
In contrast, stearic acid methyl ester content did not corre-
late well with CFPP (Fig. 3B), which increased sharply (over
0°C) when the biodiesel blend contained more than 3.5 wt%
stearic acid methyl ester. This relationship between stearic
acid methyl ester content and CFPP requires more study.
Fig. 3C summarizes the relationship between saturated
fatty acid methyl ester content in a biodiesel and its CFPP.
The total saturated fatty acid content (in this case, palmitic
plus stearic acids) correlated well with CFPP, as follows: Y
= 0.449X − 9.198 (Eq. 5), where X is the total saturated fatty
acid methyl ester content in the biodiesel, and Y is the CFPP
(°C). The regression coefficient (R
2
) was 0.917. Based on
these results, it is possible to directly estimate the CFPP of
blended biodiesels based on their saturated fatty acid ester
contents.


CONCLUSION

Since the relatively high CFPP of biodiesel critically hin-
ders its diesel engine performance during the winter season,
we simply and effectively addressed this problem by blend-
ing biodiesels from different sources: soybean, rapeseed,
palm, and lard. After studying the mathematical relationship
between the CFPP values and the blending ratios of the bio-
diesels, we could closely correlate the two, resulting in linear
equations that predicted CFPP based on saturated fatty acid
composition. These results could be enormously helpful in
selecting proper raw materials for biodiesel production, and
in ameliorating undesirable low-temperature properties of
existing biodiesels.


Acknowledgements This work is the outcome of a fos-
tering project of the Specialized Graduate School, which is
financially supported by the Ministry of Knowledge Econ-
omy. Also we appreciate Professor Cha Yong Choi of Seoul
National University to build up KSBB.


Received May 27, 2008; accepted June 25, 2008
510

REFERENCES

1. Mittelbach, M. and C. Remschmidt (2004) Biodiesel−
The Comprehensive Handbook. 1st ed., Boersedruck
Ges.m.b.H, Vienna, Austria.
2. Jeong, G. T. and D. H. Park (2006) Batch (one- and two-
stage) production of biodiesel fuel from rapeseed oil.
Appl. Biochem. Biotechnol. 129-132: 668-679.
3. Jeong, G. T., D. H. Kim, and D. H. Park (2007) Re-
sponse surface methodological approach for optimiza-
tion of free fatty acid removal in feedstock. Appl. Bio-
chem. Biotechnol. 136-140: 583-593.
4. Lang, X., A. K. Dalai, N. N. Bakhshi, M. J. Reaney, and P.
B. Hertz (2001) Preparation and characterization of bio-
diesels from various bio-oils. Bioresour. Technol. 80: 53-62.
5. Ma, F. and M. A. Hanna (1999) Biodiesel production: a
review. Bioresour. Technol. 70: 1-15.
6. Usta, N. (2005) Use of tobacco seed oil methyl ester in a
turbocharged indirect injection diesel engine. Biomass
Bioenergy 28: 77-86.
7. Kim, S. J., S. M. Jung, Y. C. Park, and K. Park (2007)
Lipase catalyzed transesterification of soybean oil using
ethyl acetate, an alternative acyl acceptor. Biotechnol.
Bioprocess Eng. 12: 441-445.
8. Lee, D. H., J. M. Kim, H. Y. Shin, S. W. Kang, and S.
W. Kim (2006) Biodiesel production using a mixture of
immobilized Rhizopus oryzae and Candida rugosa li-
pases. Biotechnol. Bioprocess Eng. 11: 522-525.
9. Krawczyk, T. (1996) Biodiesel-alternative fuel makes
inroads but hurdles remain. Inform 7: 801-829.
10. Dorado, M. P., E. Ballesteros, J. A. Almeida, C. Schel-
lert, H. P. Lohrlein, and R. Krause (2002) An alkali-
catalyzed transesterification process for high free fatty
acid waste oils. Trans. ASAE 45: 525-529.
11. Jeong, G. T., H. S. Yang, S. H. Park, and D. H. Park
(2007) Optimization of biodiesel production from rape-
seed oil using response surface methodology. Kor. J.
Biotechnol. Bioeng. 22: 222-227.
12. Park, J. Y., D. K. Kim, J. P. Lee, S. C. Park, Y. J. Kim,
and J. S. Lee (2008) Blending effects of biodiesels on
oxidation stability and low temperature flow properties.
Bioresour. Technol. 99: 1196-1203.
13. Knothe, G. (2005) Dependence of biodiesel fuel proper-
ties on the structure of fatty acid alkyl esters. Fuel Proc-
ess. Technol. 86: 1059-1070.
14. Korean Standard Association (2003) Animal and vege-
table fats and oils analysis by gas chromatography of
methyl esters of fatty acids. KS H ISO 5508.
15. Korean Standard Association (2003) Petroleum products
and lubricant determination of acid or base number: col-
our indicator titration method. KS M ISO 6618.
16. Korean Standard Association (2002) Test methods for
acid value, saponification value, ester value, hydroxyl
value and unsaponifiable matter of chemical products. KS
M 0065.
17. Kang, Y. M. and H. S. Kim (2001) Emulsified trans-
esterification of soybean oil into biodiesel. J. Kor. Oil
Chemists’ Soc. 18: 298-305.