ARTICLE IN PRESS

Biomass and Bioenergy 27 (2004) 485491

www.elsevier.com/locate/biombioe

Impact of cold ow improvers on soybean biodiesel blend

Chuang-Wei Chiu, Leon G. Schumacher, Galen J. Suppes
Department of Chemical Engineering, University of Missouri, W2028 Engineering Bldg. East, Columbia, MO 65211, USA
Received 26 September 2003; received in revised form 22 April 2004; accepted 23 April 2004

Abstract

The use of biodiesel as a diesel fuel extender and lubricity improver is rapidly increasing. An import aspect of using
these extenders is their transport in cold climates and subsequent mixing with cold diesel fuel. In this paper, the cold
ow properties of biodiesel (B100) and 80% (B80) to 90% biodiesel in kerosene were evaluated with pour point
depressants, toward the objective of identifying approaches to transport and mix biodiesel with diesel in cold climates.
Four cold ow improver additives were tested at 0.12% in B80, B90, and B100 blends. Two additives signicantly
decreased the pour points of soybean biodiesel blends, but all the four additives had little effect on cloud points.
A mixture of 0.2% additive, 79.8% biodiesel, and 20% kerosene reduced the pour point of B100 by 27 1C.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Soybean biodiesel; Diesel; Cold ow properties; Kerosene; Pour point depressant; Cold ow improver; Pour point; Cloud
point

1. Introduction temperatures near 0 1C. Soybean-based methyl

There has been a considerable interest in
developing biodiesel as an alternative fuel in recent
years due to its environmental benets and
because it is derived from renewable resources like
vegetable oils or animal fats. However, the freezing
and gelling of many biodiesel formulations are
limiting their applications. Formulations that are
high in the alkyl esters of saturated fatty acids, like
the methyl esters of beef tallow, can gel up at
Corresponding author. Tel.: +1-573-884-0562; fax: +1-
573-884-4940.
E-mail address: suppesg@missouri.edu (G.J. Suppes).
esters, the most common in the US, will become
cloudy and gel at temperatures near 0 1C and

5 1C.
These diesel fuel extenders can reach the broad-
est possible markets only if these fuel extenders are
liquid in the diesel at the cold operating tempera-
tures encountered by diesel-powered vehicles.
While much research has been conducted on
blends of 220% biodiesel in diesel to overcome
problems related to low-temperature operability,
little research has been conducted on mixtures
containing 80% (B80) and 90% (B90) biodiesel,
intended as formulations to transport and mix the
biodiesel in cold weather.

0961-9534/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2004.04.006
 ARTICLE IN PRESS
486 C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491
Cloud points and pour points have been
routinely used to characterize the cold ow
operability of diesel fuels in the petroleum
industry. Cloud points are useful as fuel quality
control specications for reners when blending
fuels during the cold climate, also, as low-
temperature operability indicators for diesel-pow-
ered operators when using in cold ambient
temperatures. At the cloud point, long-chain
hydrocarbons (or saturated fatty acid ester in
biodiesel) begin to form small wax crystals, and
when enough wax crystals with diameters exceed-
ing 0.5 mm have precipitated the fuel appears
cloudy. As temperatures decrease below the cloud
point, crystals continuously grow and agglomerate
until they are large enough to plug fuel lter
systems. Eventually, the fuel can gel up and cease
to pour even though much of the fuel has not
frozen. Pour points are useful for characterizing
the suitability of a fuel for large storage and
pipeline distribution [1,2].
ASTM standard test methods D-97, D-4539,
and D-2500 were developed to characterize the
cloud point, low-temperature lterability (LTFT),
and pour point temperatures. Of these tests, the
LTFT is often considered the most important to
characterize the suitability of a fuel for use in a
vehicle as a function of the weather.
The LTFT temperatures of a diesel fuel are
usually between its cloud and pour points. Earlier
studies showed that LTFT of biodiesel/petroleum
blends were linear functions of the cloud point,
and statistical analysis showed that an empirical
1:1 correlation existed between LTFT and the
cloud point [3].
The LTFT is believed to occur when the wax
crystals become 50250 mm in diameter, plugging
the fuel lter or gelling the fuel and making it
impossible for the fuel system to deliver fuel to the
engine [4,5]. Low-temperature operability pro-
blems generally also occur in low sulfur #2 diesel
(LSD #2) when overnight temperatures reach the
range of
101C to
15 1C [2,4], which is lower
than the 0 1C to
6 1C often observed for biodiesel
from soybean oil.
Operability temperature limits for diesel fuels
and equipment cannot be reliably predicted only
by cloud point or pour point data during cooler
weather, since cloud point commonly overpredicts
operability temperatures, whereas pour point
tends to be an overoptimistic estimate [1,2,5,6].
LTFT, which has been widely accepted in North
America, focuses on dynamic tests that simulate
ow through lters in the fuel systems, rather than
on static physical property tests like cloud points
and pour points.
Primary solutions to minimize bulk ow and
fuel lter block problems include:
 Utilization of fuel tank, fuel line and fuel lter
heaters.
 Utilization of additives (pour point depressants,
anti-gel additives, or cold ow improvers) that
enhance that impact crystal morphology.
 Blending with a fuel like kerosene which causes
freezing point depression.
Trucks used in cold climates are often outtted
with fuel tank and fuel lter heaters. Most
additives function by crystal modication, redu-
cing the size and shape of the wax crystals, but do
not alter initial formation of the crystals. Hence,
they do not generally affect the cloud point. They
inhibit the crystals from growing to a size large
enough to plug lters, and provide a barrier to
crystal agglomeration. These additives normally
have a higher price and additional cost is needed
when the additives are used to improve low-
temperature properties of biodiesel. Blending
sufcient amounts of kerosene-type components
can improve the cold ow properties of diesel fuel
blends. However, kerosenes use must be limited
because increasing amounts decrease caloric
value and fuel lubricity. An earlier study reported
that blending petroleum diesels with soybean
biodiesel could improve their low-temperature
properties [3]. Results showed that blending 20%
soybean biodiesel with No. 2 diesel, or 30%
soybean biodiesel with No. 1 diesel improved the
pour point p
10 1C. However, it is only effective
when at low ratios of soybean biodiesel.
This work evaluates the performance of addi-
tives for improving the cold ow properties of
higher blend ratios of soybean biodiesel. Neat
biodiesel and its blends with kerosene (D#1) and
low sulfur diesel fuel (LSD #2) were treated with
additives and examined by ASTM standard test
 ARTICLE IN PRESS
C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491
methods including D-97, D-2500 and D-4539. The
purpose is to identify approaches for transporting
biodiesel in cold weather and blending biodiesel
with diesel to B20 or B2 formulations.
2. Experimental procedures
2.1. Materials
MCC Soypreme (Soybean biodiesel) was pur-
chased from MidContinental Chemical Co. (Lea-
wood, KS). Low sulfur diesel and kerosene were
from the Resource Recovery Complex of Uni-
versity of Missouri-Columbia (Columbia, MO).
The following four cold ow improver additives
were selected for testing: OS-110050 from SVO
Specialty Products Inc. (Eastlake, OH); Bio Flow-
870 and Bio Flow-875 from Octel Starreon LLC
(Littleton, CO); and Diesel Fuel Anti-Gel from
Dawn Chemical Corp. (Milwaukee, WI). Many
additives contain proprietary components, in most
cases; they are mixtures of ethylene vinyl acetate
copolymers and naphthenic distillates.
2.2. Methods
Cloud point, pour point and low-temperature
ow tests characterized the low-temperature oper-
ability of diesel fuels. These measurements for
soybean biodiesel blends were carried out follow-
ing the ASTM standards D-2500, D-97 and D-
4539 procedures, respectively. ASTM D-2500 and
D-97 procedures were followed using 20 ml test
tubes instead of 150 ml beakers. Five concentra-
tions of Bio Flow-875 additive, 0%, 0.001%,
0.025%, 0.1% and 0.2%, were tested with soybean
biodiesel and D#1 blends. Seven concentrations of
OS-110050 additive, 0%, 0.1%, 0.2%, 0.5%,
0.75%, 1% and 2%, were tested with soybean
biodiesel and LSD #2 blends. A minimum of three
replicate measurements was averaged for each
data point.
2.3. Mixing procedure of soybean biodiesel blends
Soybean biodiesel was mixed with cold ow
improvers before adding it to D#1. The appro-
487
priate amount of soybean biodiesel was measured
in masses of 100, 90 and 80 g and placed into glass
asks. The appropriate amount of cold ow
improver was added to each ask (0, 0.001,
0.025, 0.1 and 0.2 g). The mixtures were mixed
thoroughly. Samples of B100, B90, and B80 blends
were created by mixing D#1 with soybean
biodiesel mixture. The soybean biodiesel and
LSD #2 blends were prepared two ways. Either
soybean biodiesel was mixed with the additive
before adding it to LSD #2, or the additive was
added to the container after soybean biodiesel had
been blended with LSD #2.
2.4. ASTM D-97 pour point procedure [7]
The observation of the samples starts at a
temperature that is at least 9 1C above the expected
pour point. The sample was immersed into an

18 1C cooling bath. If the sample had not ceased
to ow when its temperature has cooled to
6 1C,
the sample was then transferred to
33 1C cooling
bath. Readings were taken for every 3 1C decrease
in the temperature, until the sample totally ceased
ow (the sample was held in a horizontal position
for 5 s). Reading of the test thermometer was taken
and 3 1C was added to the temperature recorded as
the result of the ASTM D-97 pour point.
2.5. ASTM D-2500 cloud point procedure [1]
The same cooling procedure as described in
ASTM D-97 was followed; the samples were
examined at intervals of 1 1C, until any cloud
was observed at the bottom of the test jar. The
cloud point was reported to the nearest 1 1C as
ASTM D-2500 cloud point.
2.6. ASTM D-4539 low-temperature flow test
procedure [8]
The sample was observed starting from a
temperature that is at least 5 1C above the cloud
point of the sample (ASTM D-2500), the sample
was cooled at a rate of 1 1C/h and ltered through
a 17-mm screen under 20 kPa vacuum (150 mm
Hg). The minimum temperature at which 180 ml
can be ltered in 60 s or less was recorded.
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488 C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491

3. Results and discussion pour points. This performance is consistent with a

3.1. Cloud point and pour point studies
The cloud point is the highest temperature used
for characterizing cold ow properties and the
pour point is the lowest. Table 1 summarizes the
cloud and pour point results for a series of soybean
biodiesel blends with LSD #2 treated with OS-
110050 additive. The way the additive was mixed
(pre or post) did not appear to impact either the
cloud or pour points. There appeared to be no
benet of treatment levels beyond 0.75%.
Adding 0.75% OS-110050 additive with 70 and
80 vol% LSD #2 produced a cloud point of

15 1C and pour point of
29 1Ca signicant
reduction in these properties over the neat
biodiesel. The addition of OS-110050 additive at
the level of 0.5% in 80 vol% LSD #2 blend
resulted in the same pour point as untreated
LSD #2.
In view of the ASTM D-97, which indicates 3 1C
temperature intervals for checking the cloud point
temperature, the OS-110050 additive summarized
in Table 1 had essentially no impact on the cloud
point temperature. With more than 10 1C de-
creases in the pour point temperatures, this
additive was however effective in decreasing the
small amount of an additive being able to impact
crystal morphology but not being able to have a
signicant freezing point depression (a thermo-
dynamic phenomena).
The impacts of three additives on the cold ow
properties of B90 and B80 blends with kerosene
(D#1) are summarized in Table 2. Cloud points
changed in a linear fashion with blend composi-
tionconsistent with freezing point depression
from the blending of miscible liquids. The ad-
ditives had essentially no effect on cloud point.
A relatively small loading of 0.1% additive
produced a 6 1C decrease in pour point. Bio Flow-
875 was the most effective of these additives and
was further evaluated as summarized in Fig. 1. The
additive was more effective in the B90 and B80
blends than with B100 with the pour points of

20 1C and
30 1C being attainable in B90 and
B80 blends. This approach can be successfully
used to transport concentrated biodiesel solutions
for mixing to B20 and B2 blends.
3.2. LTFT studies
Table 2 also summarizes LTFT data for B100,
B90, and B80 treated with 0.1% Bio Flow-875
additive. Analogous to cloud and pour point

Table 1
Cloud points and pour points of blending low sulfur diesel (LSD #2) in soybean biodiesel treated with OS-110050 additive

Blend ratio Mix method (additives mixed with soybean biodiesel before Mix method (soybean biodiesel
(vol% LSD#2) blending with LSD#2) blended with LSD#2 before
adding additives)

0% 0.1% 0.2% 0.5% 0.75% 1% 2% 0.5% 1% 2%

Cloud point
0
4
7
7
4
7
4
7
60
12
12
12
15
12
15
15
15
15
15
70
12
15
12
15
15
15
15
15
15
15
80
15
15
15
15
15
15
15
12
15
15
100
18
18
15
15
18
12
12
Pour point
0
7
12
12
7
15
7
18
60
15
15
18
21
26
29
18
21
29
26
70
15
21
18
23
29
32
29
23
29
31
80
21
18
21
26
29
31
31
26
29
26
100
26
29
32
32
29
32
31
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C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491 489

Table 2 function to prevent fuel lter blockage. The Bio

Low-temperature properties of neat soybean biodiesel and
Flow-875 appears to follow this type of behavior.
soybean biodiesel/D#1 blends treated with 0.1% additive

Additive Blend ratio Cloud Pour LTFT 3.3. Impacts of additive loadings in soybean
(wt% D#1) point (1C) point (1C) (1C) biodiesel blends
None 0
1
6
2
10
3
12
4 Additives for improving the cold ow properties
20
5
15
6 of diesel fuel have been extensively studied
Bio Flow-875 0
1
9
2 [2,4,5,911]. Generally, additives are developed to
10
3
18
5 distort the crystal shape and to some extent alter
20
5
33
6 their size, or directly inhibit their growth habit,
Bio Flow-870 0 0
18 thereby reducing pour point temperatures. Many
10
4
24 additives contain proprietary components, and
20
5
30
copolymers of ethylene and vinyl acetate or other
Diesel fuel 0 0
15
olen-ester copolymers [10,4,9]. Cloud points are
anti-gel
10
4
21 not signicantly reduced because cloud points are
20
5
24 indicative of freezing that is primarily altered by
adding >5 wt% of a blend stock to produce
freezing point depressionthis freezing point
depression was observed for all blends of this
0
0% study. It is practically impossible to cause a
0.001%
-5 0.025% substance to freeze at a signicantly lower
0.10%
0.20% temperature by adding o1 wt% additive.
-10
Pour point (Celsius)

In diesel fuels, a few polymer additives having

-15
-20
-25
-30
-35
0 5 10 15
Blend Ratio (wt% D#1)
Fig. 1. Pour points of kerosene (D#1)-in-soybean biodiesel
blends treated with bio Flow-875 additive.
results, increasing blend ratios of D#1 decreased
the LTFT. Freezing point depression caused the
decreases in cloud points.
The LTFT was not signicantly affected by
0.1% additive loading, following the cloud point
temperatures and always being about 1 1C lower in
temperature. Some additives function to distort
the crystal shape from at plate-like crystals to
irregular-shaped crystals, and to some extent
reduces their size. These additives function well
to improve the bulk movement properties of a fuel,
thus, resulting in lower pour point, but they do not
long hydrocarbon chains have been observed to
delay observable crystal formation as a petroleum
diesel is cooled. These additives tend to reduce the
visibility of the crystals and not their formation.
Similar approaches will be considerably more
challenging to develop for biodiesel blends because
20 25 biodiesel has less chemical diversitybiodiesel is
comprised of fewer chemical components present
in higher composition than petroleum diesel.
Whereas petroleum diesel fuels can have o1%
solids present for 10 1C or more below the onset of
crystallization, the lack of chemical diversity in
biodiesel fuels narrows the temperature gap
between the cloud point and pour point. This
same phenomena causes the LTFT to more closely
shadow the cloud point. A similar phenomenon
was observed by Suppes et al in Fischer Tropsch
fuels [12].
The data of Table 3 summarize cold ow
properties of B5 treated with 0.05% Bio Flow-
875 additive. At these low loadings of biodiesel,
the LTFT temperatures approach the pour point
temperatures, reinforcing the afore-conclusion.
The following expression was used to quantify
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490 C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491

Table 3
Low-temperature properties of 5% soybean biodiesel blend (B5) treated with 0.05% bio Flow-875 additive

Additive DF grade Blend ratio Cloud Pour point LTFT (1C)

(vol% biodiesel) point (1C) (1C)

None Diesel No. 1 0
26
42
35

Diesel No. 1 5
28
39
35
Diesel No. 1 5
24
36
31
60% No. 1 and 40% No. 2 5
14
27
21
60% No. 1 and 40% No. 2 5
12
27
21
Bio Flow-875 Diesel No. 1 0
26
54
39
Diesel No. 1 5
29
45
39
Diesel No. 1 5
24
45
35
60% No. 1 and 40% No. 2 5
15
42
34
60% No. 1 and 40% No. 2 5
13
48
33

the LTFT temperatures as a function of the more-
easily measured cloud (CP) and pour (PP) point
temperatures:
LTFT CP
X %CP
PP:
X was t to the data with lower values of X
indicating an LTFT similar to the cloud point.
The average of X in B5 was 61.8% with no
additive loading and 60.4% when treated with
0.05% additive; the standard deviations were 6.5%
and 6.0%, respectively. For B100, B90 and B80
blends, the average of X value was 13.7% with no
additive loading and 9.8% treated with 0.1%
additive; the standard deviations were 4.5% and
4.4%, respectively. These data quantify that larger
reductions in LTFT are possible in blends with
lower loadings of biodiesel.
The two Bio Flow additives evaluated in this
study were specically designed for use with
biodiesel. These additives were more effective than
other additives known to be effective for petro-
leum diesel. The interactions of additives and wax
crystals are fairly specic [11], so a particular
additive generally will not perform equally well in
all fuels. The data demonstrate that the same
additive can (1) reduce the pour point to allow
transportation and mixing in B90 to B80 blends
and (2) reduce the LTFT of the B2 to B20 blends
that must go through the engines ltration system.
In most additives, pour points of soybean
biodiesel blends decreased with increasing additive
loading. Although this depression in pour point is
nearly proportional to additive loading, its magni-
tude varied between additives. Anomalous beha-
vior in the pour point data showed in Table 1 was
noted for loading OS-110050 in soybean biodiesel
and LSD #2 blends. At 0.2% additive loading, the
pour point decrease was only 3 1C in 70 vol% LSD
#2-in-soybean biodiesel blend, the minimum load-
ing was 0.1% and the pour point reduction was
6 1C. For 80 vol% LSD #2-in-soybean biodiesel
blend, 0.2% additive loading had the same pour
point as untreated blend; nevertheless, 0.1%
additives loading increased the pour point com-
pared to untreated blend. At 0.75% and 2%
additive loading, neat soybean biodiesel had pour
point reductions of 8 1C and 11 1C, respectively.
On the contrary, these two concentrations of
additives loading only gave pour point reductions
of 3 1C and 5 1C in pure LSD #2. Increasing blend
ratio of LSD #2 decreased the efcacy of OS-
110050.
Fig. 1 is a graph of pour point results of
blending D#1 in soybean biodiesel treated with
different loadings of the additive. Addition of
0.1% and 0.2% Bio Flow-875 additive to the neat
soybean biodiesel showed a three-degree decrease
in pour point for every 0.1% increase in the
additive, which means that the additive only could
show little effect on neat soybean biodiesel. The
results of 10 and 20 wt% D#1 blends with 0.001%
and 0.025% additive loadings affected the pour
point; however, 0.2% additive showed no signi-
cant change when compared to 0.1% additive
 ARTICLE IN PRESS
C.-W. Chiu et al. / Biomass and Bioenergy 27 (2004) 485491
loading. It indicates that the additives could
signicantly affect the soybean biodiesel/D#1
blends only when its loading is lower than 0.1%.
Cold ow improver additives can reduce pour
point temperatures in biodiesel blends. These
additives and 1020% bending with a petroleum
fuel are particularly effective when transporting
biodiesel with subsequent blending to B20 or B2.
When the proper additives are used, tank and fuel
line heating systems can be averted. In addition,
additives can be used to substantially reduce the
use of kerosene to winterize diesel fuel. There are
no lubricity issues with kerosene (D#1) and
soybean biodiesel blends, since soybean biodiesel
is a lubricant and will be able to lubricate kerosene.
Acknowledgements
We acknowledge Paul Oien of the South Dakota
Department of Transportation for providing B5
samples. SVO Specialty Products INC. (Eastlake,
OH), Octel Starreon LLC (Littleton, CO), and
Dawn Chemical Corp. (Milwaukee, WI) provided
the cold ow improver additives for this project;
their support is greatly appreciated.
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