Effect of additives to improve the performance of biodiesel at low temperatures

Evaluation of a novel type of chemistry to improve the Cold Filter Plugging Point of Fatty Acids Methyl Esters

Lopes, P.M. 1; Muller, D.1; Harrison, R.1; Bordado, J.C.2

1 Arizona Chemical B.V., European Oleochemicals Research & Development Group, Almere, The Netherlands

2 Instituto Superior Técnico, Departamento de Engenharia Química, Lisboa, Portugal

Abstract: Using several experimental techniques, such as differential scanning calorimetry (DSC), thermomiscroscopy and
determination of cloud point (CP), pour point (PP) and cold filter plugging point (CFPP), polyamides were tested in fatty
acids methyl esters (FAME) obtained from vegetable oil triglycerides and fossil diesel fuel as a cold flow improver (CFI)
additives. The methyl esters were derived from rapeseed, soybean and palm oil feedstock, and the prototype polyamide
additive was benchmarked against industry standard ethylene vinyl acetate (EVA) additives. The experimental results
showed that the polyamide additive was very effective in the depression of the CP and PP of rapeseed methyl esters (RME).
This work also supports the state of the art knowledge regarding the fact that the effectiveness of CFI additives is decreased
with the blend of esters derived from vegetable oils with higher concentration of saturated fatty acids in the fatty acid profile.
Given that the polyamide CFI additive is formulated in a matrix of free fatty acids (FFA), it possesses unique properties since
it was established that it also provides lubricity and anti-corrosion to ultra low sulphur diesel fuel.

Keywords: biodiesel, cloud point, cold filter plugging point, cold flow improvers, crystallization of saturated fatty acids,
diesel fuel, kinematic viscosity, low temperature properties, methyl esters, polyamides, pour point.

1. Introduction emitted from the combustion of an equivalent amount of

It is a well established fact that the methyl esters
obtained from vegetable oil and animal fats lipids
(triglycerides) can be used to power compression-ignition
(diesel) engines. In fact, Rudolph Diesel, inventor of the
engine with the same name, ran the prototype presented
in the 1900 World Exhibition of Paris on peanut oil
(Knothe, 2001). Triglycerides are too viscous to enable
an effective injection in modern diesel engines, but by
promoting the transesterification of these materials in the
presence of methanol and a catalyst, the properties of
the FAME compares very well with fossil diesel, in terms
of cetane number, viscosity and enthalpy of combustion
(Suppes, 2005). Biodiesel is a material that is readily
degradable through biological processes if spilled on the
environment and, because has very high flash points
(above 150°C), this fuel is safer to handle and store
compared with fossil fuels. Additionally, the combustion
of FAME lower the amount of hazardous materials that
are released to the atmosphere, such as particulate
matter, carbon mono and dioxide, sulphur oxides
compounds, etc. The only increase in the emissions is
related with NOx, due to the lower combustion
temperatures that are registered in the engine cylinder
chambers (McCormik, 2003). Until very recently, the
utilization of FAME was also said to have either a
negative or zero carbon footprint, meaning that the
overall carbon released to the atmosphere during the
preparation of the fields, planting, fertilization, cropping,
transportation of the crops, transesterification and
combustion of the final biodiesel fuel is less than the CO2
fossil diesel, since the fossilized plants deceased million
of years ago do not possess a present counterpart to
absorb the carbon during the plant’s growth (van de
Heuvel, 2005). However, more recent studies are
demonstrating, to much controversy, that in fact there is
an effective increase in the carbon by utilizing biodiesel
as a fuel (Doornbosch, 2007)‡. The low temperature
performance is a crucial technical parameter that renders
problematic the utilization of FAME in diesel engines in
regions of moderate temperature. The performance
issues of diesel fuel derived from the formation of
crystalline structures at low temperatures are known for
many decades by refineries and engine manufacturers.
a) b) c)
Fig. 1 - Different crystal morphologies: a) plate, b) irregular and
c) need shape.
In fossil diesel fuel, the main crystalline structures are
formed by linear, branched or cyclic hydrocarbons. Pure
paraffin crystallizes as monoclinic (chains larger than
C26), triclinic (chains shorter than C26) or orthorhombic
‡
. However, the detailed discussion of the Carbon Footprint and Life
Cycle Assessment (LCA) is being the scope of this paper.
Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel
(chains with odd number of carbon atoms) structures
(Marie, 2005). These considerations are however far
from applicable to a common fuel matrix: due to the
complexity and number of different molecular species,
crystals are never derived from pure but from material
with a broad distribution of carbon chain lengths. A study
showed that the paraffinic material present in diesel
fuels, when crystallizes out of solution, is enriched with
the higher molecular weight paraffin with respect to the
composition of the initial mixture (Marie, E. et al, 2004).
In the case of biodiesel, as the methyl esters are cooled
towards its melting point, the fuel will initially become
cloudy and upon further cooling, the viscosity will
increase until reaching complete solidification. There are
three main parameters that can be used to evaluate the
performance at low temperatures of a fuel: cloud point,
cold filter plugging point and pour point.
 Cloud Point
The cloud point (CP) is defined as the temperature at
which crystals first appear in the fuel, and the ASTM
D2500 is the standard method for this determination. It is
well established that heavy n-alkanes and saturated
methyl esters are, respectively, responsible for the CP of
diesel and biodiesel fuels (Dunn, R.O., 2004). This
transition corresponds to an equilibrium controlled by
kinetics (crystal side) and thermodynamics relationships
(solvent side), and although initially the crystals are
submicron in size and invisible to the human eye, as
temperatures drop further, the particles will reach
approximately 0.5 m in size and the crystals will
become visible and the fuel will appear as turbid.
 Pour Point
As temperature drops further below the CP, the crystals
formed will begin to agglomerate first and form
aggregates afterwards. This eventually leads to complete
solidification, and the fuel, behaving now more like a
solid, is no longer able to flow, i.e., no longer pourable
(Dunn, R.O., 1996). This point, measured accordingly to
ASTM D97, is defined as the Pour Point (PP), and can
occur with as little as 1.0 to 2.0 weight percent of
precipitated material.
 Cold Filter Plugging Point
As effective measures of the fuel ability to be used in
“real life” situations, the CP and PP are not acceptable.
Upon closer look, the CP can be considered as a
“pessimistic” value, since the fuel, even though revealing
some turbidity, is still able to flow freely and no issues
are expected to occur to the mechanic components. On
the other hand, the PP is an “over optimistic” value: it is
more than certain that a fuel that has reached this point,
not only will not flow through the fuel injection system,
but most probably already caused severe operational
issues, such as completely plugged fuel lines and engine
shutdown due to fuel starvation. Therefore, due to the
need of having a parameter that correlate well with “real
Arizona Chemical / Instituto Superior Técnico, September 2007
life” situation, the Cold Filter Plugging Point (CFPP) was
created, correlating to the temperature at which a fuel will
plug a 45 m filter (similar mesh opening as installed in
vehicles) under standardized injection pressure
conditions. There are three main methods to improve the
performance of biodiesel at low temperatures:
winterization blends with fossil diesel and utilization of
CFI additives.
 Winterization
Winterization is a popular technique used to reduce the
CP of vegetable oils in the food industry and used
extensively in the manufacture of salads and other
dressing’s formulations. One common technique for
industrial winterization of biodiesel is to carefully control
the refrigeration rate of large storage tanks for a well
defined period of time. Afterwards, the liquid portion is
separated from the partially solidified material that has
settled at the bottom. From a conceptual standpoint, this
procedure could be employed in biodiesel production in
order to improve the LTP. It has been demonstrated
experimentally that winterization improves the low
temperature operatibility of FAME. Winterization
increases the iodine value, since the remaining species
in the fuel are unsaturated. As a trade-off, the oxidative
stability is extensively decreased. Winterization also
decreases the cetane number of the winterized fuel
(Dunn, 1997).
 Blends with Fossil Diesel Fuel
The route of improving the low temperature performance
of a fuel by means of diluting with a second fuel with
better LTP is well known and used for many years in the
petrochemical industry. Refiners have obtained fossil
diesel fuel with excellent performance at low
temperatures by blending it with kerosene (aviation fuel).
However, this is a simple remediation solution, since by
diluting the fuel with lighter streams, wax-related
problems can be minimized, but not eliminated. The main
economical issue related with this procedure is the cost
penalty that refineries have to accept from displacing
large volumes of a far more profitable fuel to another
market (Dunn, R.O., 1995). In the same manner as
blending vegetable oil with diesel reduces the viscosity,
blending biodiesel with fossil diesel causes an
enhancement in the LTP of the biodiesel, due to the
dilution of the fraction of saturated long-chain methyl
esters in biodiesel, therefore lowering the CP and PP
(Johnson, 2004).
 Utilization of CFI Additives
It is known that the crystal morphology and/or growth
rate is profoundly affected by the presence of impurities
in the system. Some impurities suppress growth while
some others stop growth completely in one or more
directions. Some theoretical models have been
established that centre the action of the impurity on
certain crystallographic faces of the structure, and
2
Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel
therefore impurities can also be used to modify the
crystal habit (Kubota, 2001). When impurities are added
specifically to produce a well defined and desired
morphological effect on the crystalline structure, they are
then referred as additives. The concentration at which
the additives will impart an effect varies, depending on
the particular system. An important class of additives is
so called “tailor-made” additives, which are designed to
interact in a very specific way with selected faces of
crystalline materials. These additives are designed to
contain some chemical groups (moieties) that mimic the
solute molecule and are therefore readily adsorbed at
growth sites on the crystal surface. Impurities and
additives operate by binding to growth sites and thereby
modifying the crystal growth rate. The overall shape of
the growing crystal is determined by the relative rates of
growth of its various faces. The slower the growth rate,
the larger will be the face. The individual crystals faces
will also have their own growth-rate dependence on
temperature and super saturation (Hatakka, 2006).
Additives to improve the LTP of fossil diesel fuel have
been used since the 1960´s (Brown, 1990). Despite the
additives companies claiming otherwise, the additives
used until recently in FAME are not novelty chemical
species, but instead adjustments from the historical fossil
diesel CFI additives chemistries (Lopes, 2005). The most
common type of wax crystal modifiers used to enhance
the LTP of diesel is based on ethylene vinyl acetate
(EVA) copolymer chemistry. Due to the polymerization
flexibility, these compounds can vary in molecular weight
and acetate ratio in order to obtain a polymer specifically
to a given fuel. It is known that the performance of an
EVA copolymer can be enhanced by blending with a CFI
additive of different chemistry. Other species, such as
vinyl acetate-fumarate copolymers, styrene-esters
copolymers, diester-alpha olefin copolymers, malan-
styrene esters and polymethacrylates are also used for
this porpoise. As mentioned, it has long been established
that trace amounts of specific impurities can greatly
affect crystallization. Petroleum companies have
developed specific polymeric additives to both enhance
wax nucleation (to produce many small crystal rather
than a few big ones) and slow crystal growth. Based on
macroscopic evidence, it is generally believed that
impurities bond preferentially to specific faces on the
growing crystals, inhibiting therefore the growth along
those faces. Recently, a more complex model has been
proposed, designated by kinetic growth inhibition. It was
found that the solidification can occur in the form of
macroscopic bands (with several hundred micrometers)
parallel to the front. In this growth mode, the front
periodically stops growing, allowing a new front to
nucleate and spread laterally along the arrested front.
These bands are controlled by the thermodynamics of
the process, hence the designation of the effect. As the
crystallization proceeds, solute is depleted near the front,
and as the sample moves though the gradient, a region
ahead of this depletion zone becomes supersaturated, a
situation designated as constitutional supercooling.
However, if a kinetic inhibitor additive is present, the
Arizona Chemical / Instituto Superior Técnico, September 2007
crystals do not grow appreciably (Alkane Crystalization
Theory, 2007). The interaction between the additives and
the crystals in the fuel may take place either in solution,
at the surface or inside the crystalline structure, in the
case of co-crystallization.
2. Experimental
2.1 Methods
Cloud/Pour Point Measurements.
The measurements were carried out on a Herzog HCP
852 apparatus. The experimental conditions are
described on test methods ASTM D2500 and ASTM D97
standards, respectively, for the determination of the CP
and the PP.
Cold Filter Plugging Point Measurements.
The measurements were carried out on a Herzog HCP
842 apparatus. The experimental conditions are
described on test method ASTM D6371.
Chromatography Analysis.
GC-FID on fatty acid composition according to internal
procedure AQCM022.
Corrosion.
The corrosion was assessed by the petrochemical
industry standard NACE TM0172 test method.
Differential Scanning Calorimetry (DSC).
The measurements were carried out sing a standard
Mettler apparatus. The sample was placed in a 40 µl
aluminum pan (approximately 10 mg sample mass) and
the temperature program ran as follows: 25 °C to -65 °C
with a cooling rate of -5 K/min and -65 °C to 40 °C with
two heating rates of +2 and +5 K/min, under an
atmosphere of 50 ml/min N2. The calorimeter signal was
recorded and stored to be used off-line.
Lubricity.
The lubricity parameter was measure by the High
Frequency Reciprocating Rig (HFRR) method in the
petrochemical laboratories of the OBR refinery in Poland,
according to ASTMD6079.The parameter assessed was
the Wear Scar Diameter measured in millimetres.
Thermomicroscopy.
This type of investigation is excellent for providing the
correlation between morphological changes with the
thermal effects observed with DSC experiments. The
equipment used was a DSC823e with intracooler and a
hot stage (Mettler FP82) with circulating liquid nitrogen for
cooling. This equipment can operate can operate in the
range from -70°C to +300°C, controlled by a FP80 control
unit. The samples were placed between glass slides for
the microscope camera. The temperature ranged from
+25°C to -60°C with a cooling rate of -5 K/min. The
magnification used was of 6.5 times.
3
Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel

2.2 Products terminated polyamides (ETPA) and tertiary amide

terminated polyamide (ATPA).
The biodiesel samples were obtained from leading EU
producers, such as ADM (Leer and Hamburg in O O O O
Germany), INEOS (Verdun in France), etc. Given the R1 O C Dimer C NH-CH2CH2 NH C Dimer C O R1
nature of the work, these samples did not contain any n
kind of additives. The fossil diesel fuel was obtained from Ester Terminated Polyamide (ETPA)
GALP Refinery in Sines, Portugal, and no additives were R2
O O O O
R2
present in the fuel. The polyamide material tested was N C Dimer C NH-CH2CH2 NH C Dimer C N
part of the current Arizona Chemical’s portfolio and the R1 n R1
benchmarking EVA additives are commercial products
offered by leading companies in the area of fuel Tertiary Amide Terminated Polyamide (ATPA)
additivation.
Fig. 2 - Polymeric structure of two types of polyamides from
Arizona Chemical (AZC) portfolio.
2.3 Protocol The results from the initial evaluation of the CP and PP
of the polyamides are presented in the following table.
The experimental analysis can be divided in two main
stages: an initial screening exercise where a great Table 2 – Experimental results of the behaviuor of RME dosed
number of polyamide material was tested to establish a with diffrent concentrations of different additives.
correlation between chemistry/performance and a
second stage, where the optimal carrier solvent and treat Polyamide RME
rate of the polyamide was evaluated and benchmarked treat rate
Cloud point Pour Point
with commercially available CFI additives. The Additive (°C) (°C)
(ppm)
performance of the Arizona Chemical prototype additive -3 -12
was also evaluated in fossil diesel fuel. 200 -4 -17
300 n.a. -18
400 n.a. -36
500 -6 -38
3. Results and Discussion AZC (B) 1000 -6 -36
2000 n.a. -36
3.1 Stage One of the Polyamide Evaluation 3000 n.a. -34
4000 n.a. -23
5000 -8 -18
Besides RME, the fatty acid profile of soybean methyl AZC (A) 500 -5 -15
esters (SME) and tall oil fatty acids methyl esters (TOFA 500 -7 -15
ME) was measured by GC. AZC (H) 2000 -7 -18
5000 -8 -18
Table 1 – Fatty acid profile of TOFA ME, RME and SME AZC (I) 1000 -4 -12
500 n.a. -36
AZC (J)
Fatty Acid TOFA ME RME SME 1000 n.a. -36
(%) (%) (%) 200 n.a. -15
C16:0 Palmitic 0.20 3.79 9.11 300 -6 -15
Oleic (C18:1 - 9 cis) 26.30 30.68 22.32 AZC (K) 400 n.a. -18
Linoleic C18:2 cis 9, cis 12 40.23 21.56 51.78 500 n.a. -35
Others 0.38 8.47 6.43 1000 n.a. -36
Total Saturated Content 2.15 5.74 14.56 500 -6 -36
AZC (L)
1000 n.a. -36
500 n.a. -18
AZC (M)
1000 n.a. -33
A total of seven different samples were selected for the AZC (N) 1000 -6 -24
initial evaluation, the criteria used based the molecular 500 -6 -15
weight, the degree of dimer hydrogenation and type of Commercial 2000 n.a. -21
polymer termination group. These samples are referred Additive 1 5000 -8 -30
10000 -8 -36
as samples A to G. Additives A and B are polyamides
polymers based on ethylene diamine (EDA),
hydrogenated dimer and terminated with an amine
group, the main difference being the molecular weight Based in these experimental results, it was confirmed
(additive A lower). Additives C, D, E, F and G are similar that the polyamide with the best CFI performance were
in structure to polyamides utilized in the formulation of the ATPA type, with additive B providing the best cost
flexographic inks, the differing aspect being the structure and being therefore the preferred additive. A
molecular weight and overall formulation cost. The more in-depth concentration analysis was conducted with
following figure indicates the polymer structure of ester this additive, the optimal treat rate of the being
established at approximately 500 ppm. Further increase

Arizona Chemical / Instituto Superior Técnico, September 2007 4

 Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel

in the concentration of this additive causes a decrease in
the response. This is completely the opposite to the
response of increase in concentration of CFI additives
known to the art. It was also verified experimentally that
the EVA copolymer additive gave a linear response in PP
depression with the increase in concentration. It was
surprising to observe that the commercial additive
required nearly six times the concentration of additive B
to produce similar PP depressing effect. The following
figure indicates the response in terms of PP depression
with increasing treat rate of RME with additive B and the
commercial additive 1.
0 1000 2000
-10
PP(°C)
An extensive test program was performed to determine
the best polyamide/TOFA blend ratio, in order to
maintain the system in solution and still have a treat rate
not high to dose the right amount of active ingredient,
i.e., 500 ppm. Based on a polyamide/TOFA ratio of
45/55, the treat rate was of 1500 ppm. In the following
figure are the experimental results obtained from the
DSC experiments with neat RME and three experimental
additives.
3000 4000 5000
[Additive]
(ppm)

-20

1500 ppm
Additive B

-30

-40
Fig. 5- Comparative experimental DSC results with neat RME
Additive B RME Commercial and three AZC experimental additives.

Fig. 3- Comparison of the PP depressant effect with the treat

From the previous figure, the addition of additives not
rate for additive B and an EVA commercial additive. only creates a shift on the onset temperature of
crystallization, but also leads at a narrowing of the peaks,
clearly showing the active effect of the additives during
3.2 Stage Two of the Polyamide Evaluation the crystallization process. This effect is also observable
from the thermo microscopy results §. The current trend
The polyamides have the consistency of a viscous gel at
in the biodiesel industry is to blend FAME obtained from
room temperature and, in order to allow an accurate treat
different vegetable oil sources. The following table
level, must remain liquid at low temperature. Several
presents the effect of the addition of AZC prototype
different carrier solvents were evaluated: fossil diesel,
additive and a second commercial additive designated 2.
terpenes (α-, β-pinene and δ-3-carene), ethanol,
isosteryl-alcohol and n-heptane. However, the material Table 3- Effect of CFI additives in biodiesel obtained from
that gave better performance in disrupting the hydrogen different vegetable oil feedstocks.
bonds between the polyamide polymer chains was
TOFA. Sample
Additive
Treat rate CP PP CFPP
Description (ppm) (°C) (°C) (°C)
- 0 -5 -13 -10
Physica (Beaker Spindle) Viscosity 70% RME
1400
+ AZC´s prototype 1500 -5 -18 -10
30% SME Commercial
1200 1500 -3 -39 -14
Additive 2
1000 - 0 1 -1 -5
Viscosity (mPa.s)

80% SME
800 + AZC´s prototype 1500 1 -2 -6
20% PME Commercial
600 1500 2 -3 -6
Day 0
Additive 2
400 24 h 60% RME - 0 -3 -5 -6
48 h +
200 30% SME AZC´s prototype 1500 -4 -8 -5
+ Commercial
0
10 PME 1500 -4 -26 -5
0 10 20 30 40 PA (w t.%) 50
Additive 2

It can observed from the previous table that the increase

Fig. 4- Viscosity study of TOFA and additive B blends. in the incorporation of methyl esters derived from

§
However, given the type of image capture process, the results are not
clearly visible if paste to the body of text of this paper.

Arizona Chemical / Instituto Superior Técnico, September 2007 5

Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel

vegetable oils with higher concentration of saturated approximately 15 °C. Driven by environmental legislative
material leads both to an increase in the low temperature resolutions, the sulphur content of fossil diesel has been
parameters and a decrease in the response of the fuel increasingly targeted as a parameter to ban. Currently,
additives tested. refineries use very “aggressive” hydro-desulphurization
processes to meet the stringent maximum sulphur
content level (15 ppm in EU). This desulphurization
3.3 Effect of the additive in fossil diesel process, however, also removes aromatic species and
other naturally occurring molecules present on diesel fuel
and responsible for the naturally good lubricity of this
The additive was also evaluated in diesel fuel, the results fuel. Associated with the increasing injection pressures of
presented in the following table: the modern compression-ignition engines (such as the
new common-rail systems), the lower lubricity of this
Table 4– Performance of the additive in ULSD
Ultra Low Sulphur Diesel (ULSD) fuel creates a very fast
wear of the injector’s tips and injector pumps. Given the
Additive CP PP CFPP
(ppm) (°C) (°C) (°C) formulation of the AZC prototype additive, based on
0 -8 -12 -13 TOFA as the carrier solvent, the fossil diesel samples
1500 -8 -27 -12 treated with this additive were evaluated to determine if
there was an increase in the lubricant properties of the
sample.
Analysing the experimental results from the table 4, there Table 6 – Experimental results from the addition of 500 ppm of
is a clear improvement of the PP of the fossil diesel fuel, AZC prototype additive to ULSD
meaning that the ATPA based additive is also able to
Parameter / Method Neat Fuel + AZC Prototype Additive
disrupt the crystal growth and agglomeration of n-
PP (°C) -12 -27
paraffinic material. Based these results, it was expected HFRR (m)
595 340
that, since the additive depresses the PP of biodiesel (EN ISO 12156)
and also of fossil diesel, it should also be effective in NACE (TM0172) C A

depressing the PP of blends of both fuels. In the refining

industry these blends are referred as Bxx blends, where Observing the experimental data from table 6, it
becomes evident the positive effect in terms of lubricity
the XX index refers to the volumetric percentage of
derived from the addition of as little as 500 ppm of the
biodiesel added to fossil diesel. For instance, B2 and B5 AZC prototype additive. In fact, the European EN 590
refer to blendes of, respectively, 2.0 and 5.0% (v/v) and specification states a minimum of 460 m of scar
B100 to neat FAME. The results of the addition of the diameter measured by HFRR for ULSD fuel. With 595
AZC prototype additive into Bxx blends are presented in m, the base fuel was much above this value, but after
the following table: the addition of 500 ppm of the additive, the wear scar
diameter measured dropped to 340 ppm. A surface
Table 5- Performance of the AZC prototype additive in diesel +
phenomenon that it is closely related with lubricity is the
RME biodiesel Bxx blends ability of a molecule to provide also corrosion inhibition
properties. This parameter was measured by means of
Without Additive Additive @ 1500 ppm the current state of the art NACE procedure in the
Bxx CP PP CFPP CP PP CFPP laboratories of OBR refinery, Poland. The qualitative
(v/v.%) (°C) (°C) (°C) (°C) (°C) (°C) results indicate a clear improvement in terms of the
0 -3 -9 -14 -3 -9 -14 ability of the additized fuel to prevent metallic surfaces of
100 -3 -10 -7 -3 -10 -7 undergoing electrochemical corrosion.
2 -4 -10 -7 -6 -28 -5
5 -5 -10 -7 -2 -28 -5
10 -4 -13 -6 -5 -28 -5
20 -4 -13 -6 -5 -28 -6 4. Conclusions

Based on the experimental results, the AZC prototype

Analysing the previous table, there is apparently
contradictory behaviour when FAME is added into fossil
diesel, since there is a depression of the PP. This is due
to the fact that the biodiesel used was rapeseed, with
very good performance at low temperatures, while the
fossil diesel fuel was obtained from a summer grade
batch from a Southern European country (Portugal). The
expected PP depression behaviour could be observed,
meaning that up to 20% (v/v) of FAME added to fossil
diesel, it was still possible to lower the PP by
cold flow improver additive, formulated with ATPA
polyamide polymer dispersed in a TOFA matrix is able of
depressing the PP and CP of rapeseed methyl esters
and also of fossil ULSD. It was demonstrated that the
addition to RME of methyl esters derived of highly
saturated vegetable feedstocks, such as soybean and
palm oil, introduces an added difficulty for additives to
improve the low temperature performance of these
biodiesel blends. In fact, not even additives based on the

Arizona Chemical / Instituto Superior Técnico, September 2007 6

Effect of Additives to Improve the Performance at Low Temperatures of Biodiesel

well established EVA polymers were able to improve the
LTP of blends of SME and PME. Derived from its
composition, the additive introduces unique properties for
a CFI, namely a remarkable improvement in the lubricity
and in terms of surface protection towards corrosion.
Knothe, G. (2001). Historical Perspective on Vegetable Oils Based
Diesel Fuels. Illinois: U.S. National Centre for Agricultural Utilization.
Kubota, N. (2001). Effect of Impurities on the Growth Kinetics of
Crystals. Department of Chemical Engineering, Iwate University , 749-
769.

Acknowledgements Lopes, P. (2005). Biodiesel - Overview of Solutions to Improve the

Performance at Low Temperatures. Technology Forum. Almere, The
Netherlands: Arizona Chemical.

The author acknowledges the excellent work conducted
by Mettler-Toledo (M. Zappa, Dr. R. Riesen and K.
Schaap) in terms of the thermo microscopy analysis. The
ULSD sample could only be obtained from the diligent
work of Dipl. Eng. Eurico Correia of Galp Energia
trefinery in Sines.
Marie, E. e. (2005). Control of n-alkanes Crystallization by Ethylene
vynil-Acetate Copolymers. Journal of Colloid and Interface Science ,
290-295.
Marie, E. et al. (2004). Settling of Paraffin Crystals in Cooled Middle
Distillate Fuels. Journal of Colloid and Interfacial Science , 269-274.

McCormik, R. e. (2003). NOx Solutions for Biodiesel - Final Report.

National Renewable Energy Laboratory Report NREL/SR-510-31465 .
5. References
NACE TM0172 - Test to Assess the Anti-corrosion properties of
petrochemical materials.
Alkane Crystalization Theory. (2007). Retrieved June 2007, from
Suppes, G. e. (2005). Multifunctional Diesel Treatment Additive from
www.physics.uwo.ca
Vegeable Oils. University of Kansas: Department of Chemical and
Petroleum Engineering.
ASTM D97 - Determination of the Pour Point

van de Heuvel, E. (2005). What is the Actual Environmental and CO2

ASTM D2500 - Determination of the Cloud Point
balance for Biofuels? International Fuel Quality Centre Biofuel
ASTM D6079 - Determination of the lubricity properties my means of Technology and Policy Briefing.
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