Progress in Energy and Combustion Science 35 (2009) 481489

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Effects of minor constituents on cold ow properties and performance

of biodieselq
Robert O. Dunn*
Food and Industrial Oils Research, United States Department of Agriculture (USDA), Agricultural Research Service (ARS), National Center for Agricultural Utilization Research
(NCAUR), Peoria, IL, United States

a r t i c l e i n f o a b s t r a c t

Article history: Biodiesel is an alternative fuel or extender made from renewable agricultural lipids that may be burned
Received 25 March 2009 in a compression-ignition (diesel) engine. It is dened as the mono-alkyl esters of fatty acids derived
Accepted 14 July 2009 from plant oils or animal fats. Biodiesel has many important technical advantages compared to petro-
Available online 19 August 2009
diesel including superior inherent lubricity, low toxicity, high (non-ammable) ash point and biode-
gradability, very low or negligible sulfur content and lower exhaust emissions of most regulated species.
Keywords:
Biodiesel is generally produced by transesterication of the lipid with a short-chain monohydric alcohol.
Cloud point
This process may leave behind very small (trace) concentrations of minor constituents such as saturated
Cold soak ltration test
Low-temperature ow test monoacylglycerols (MAGs) or free steryl glucosides (FStGs). These materials have high melting points and
Monoacylglycerol very low solubilities allowing them to form solid residues when stored during cold weather. Blending
Solid residues with petrodiesel exacerbates the problem. Settling solid residues were found to clog fuel lters in fuel
Steryl glucoside dispensers and vehicles. In response to documented problems the biodiesel industry in the United States
collaborated with the American Society of Testing and Materials (ASTM) to develop a cold soak lter-
ability performance test that will help identify fuels that may have a propensity to clog lters if exposed
to long-term storage in cold weather.
Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
2. Cold flow properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
3. Minor constituents and low-temperature performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
3.1. Analysis of acylglycerols and steryl glucosides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
3.2. Effects on cold flow properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
4. Cold soak filterability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
5. Removing solid precipitates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488

1. Introduction [1,2]. In the United States, the fuel must meet specications
outlined in ASTM D 6751 (see Table 1) before it may be blended
Biodiesel is dened as an alternative fuel composed mainly of with petroleum-derived diesel fuel (petrodiesel) for use in a diesel
mono-alkyl fatty acid esters derived from plant oils or animal fats engine [3]. An engine that is fueled by biodiesel that does not
initially meet the fuel specications may develop operational
q The use of trade, rm, or corporation names in this publication is for the problems due to prematurely compromised fuel quality. The
information and convenience of the reader. Such use does not constitute an ofcial European transportation market has many more years of experi-
endorsement or approval by USDA or ARS of any product or service to the exclusion
ence with biodiesel. The biodiesel fuel specication issued by the
of others that may be suitable.
* Tel.: 1 309 681 6101; fax: 1 309 681 6340. European Committee for Standardization (CEN) is designated as EN
E-mail address: robert.dunn@ars.usda.gov 14214 [4].

0360-1285/$ see front matter Published by Elsevier Ltd.

doi:10.1016/j.pecs.2009.07.002
482 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489

Table 1
ASTM D 6751-08 standard specication for biodiesel fuel blend stock (B100) for
Nomenclature
middle distillate fuels.

Blend ratio volume percent of biodiesel in blend with Property Test method Limits Units
petrodiesel (e.g., B50 50 vol% blend) Flash point (closed cup) ASTM D 93 93 min 
C
CFPP cold lter-plugging point Alcohol Control one of the
following must be met:
CP cloud point
1. Methanol content EN 14110 0.2 max Mass%
CSFT cold soak ltration test 2. Flash point ASTM D 93 130.0 min 
C
DAG diacylglycerol (diglyceride) Water and sediment ASTM D 2709 0.050 max Volume%
FAME fatty acid methyl esters Kinematic viscosity, 40  C ASTM D 445 1.96.0a mm2/s
Sulfated ash ASTM D 874 0.020 max Mass%
FPT lter-plugging tendency
Sulfur ASTM D 5453 0.0015 (S15)b Mass% (ppm)
FStG free (non-acylated) steryl glucoside 0.0500 (S500) Mass% (ppm)
FT-IR Fourier transform-infrared spectroscopy Copper strip corrosion ASTM D 130 No. 3 max
GC gas chromatography Cetane number ASTM D 613 47 min
LTFT low-temperature ow test Cloud point (CP) ASTM D 2500 Reportc 
C
Carbon residue ASTM D 4530 0.050 max Mass%
MAG monoacylglycerol (monoglyceride)
Acid number ASTM D 664 0.50 max mg KOH/g
MP melting point Cold soak lterability Annex A1; 360 maxd Seconds
MS mass spectrometry ASTM D 7501
PP pour point Free glycerin (glycerol) ASTM D 6584 0.020 max Mass%
Total glycerin (glycerol plus ASTM D 6584 0.240 max Mass%
SME soy methyl ester methyl esters of soybean oil-
glycerol component in
fatty acids MAG, DAG and TAG)
TAG triacylglycerol (triglyceride) Phosphorus content ASTM D4951 0.001 max Mass%
Total glycerol total mass glycerol plus glycerol component of Oxidation stability EN 14112 3 min Hours
MAG, DAG and TAG Sodium and potassium, EN 14538 5 max ppm (mg/g)
combined
ULSD2 No. 2 ultra-low sulfur petrodiesel fuel
Calcium and magnesium, EN 14538 5 max ppm (mg/g)
combined

Distillation temperature, ASTM D 1160 360 max C
atmospheric
The main components of biodiesel are the mono-alkyl fatty acid equivalent temperature,
90% recovered
esters of renewable plant oils or animal fats. The chemical struc-
tures of these oils are characterized as triacylglycerols (TAGs) con- ASTM American Society of Testing and Materials; EN Test method published by
the European Committee for Standardization (CEN); MAG monoacylglycerol;
sisting of long-chain fatty acid groups attached by an ester linkage
DAG diacylglycerol; TAG triacylglycerol.
to a glycerol (1,2,3-propanetriol) backbone. They are converted to a
The 6.0 mm2/s upper viscosity limit is higher than for petrodiesel and should be
biodiesel by transesterication with a short-chain monohydric taken into account when blending.
b
alcohol such as methanol or ethanol, normally in the presence of Maximum sulfur content for ultra-low sulfur diesel (ULSD).
c
catalyst and elevated temperature. A schematic diagram of the The CP of biodiesel is generally higher than petrodiesel and should be taken into
account when blending.
generalized reaction mechanism for transesterication is shown in d
B100 intended for blending into petrodiesel that is expected to give satisfactory
Fig. 1. The process generally follows three steps where each fatty vehicle performance at fuel temperatures at or below 12  C shall comply with
acid group is sequentially removed and converted into a fatty acid a cold soak lterability limit of 200 s maximum.
alkyl ester (biodiesel) molecule [5]. As shown in Fig. 1, reaction (1)
converts TAG plus alcohol into diacylglycerol (DAG) plus fatty acid
alkyl ester. Subsequently, reaction (2) generates monoacylglycerol The present review examines available scientic literature and
(MAG) and another fatty acid alkyl ester. Lastly, reaction (3) summarizes the effects of minor constituents present in biodiesel
generates glycerol and a third fatty acid alkyl ester. Thus, at on the ow properties and performance during cold weather. Some
complete conversion one mole of TAG will generate three moles of constituents may be present in the crude lipid feedstock and be
biodiesel. Transesterication reactions are reversible and a molar carried through after conversion to biodiesel. Other constituents
excess of alcohol is usually supplied to drive the mechanism may be present due to incomplete conversion and processing of the
towards the desired products. If methanol is employed, the reaction biodiesel product. Emphasis is placed on constituents that form
mixture is biphasic at the beginning because methanol is sparingly solid residues during cold weather that have been observed to
soluble in triacylglycerol oils. The product mixture is also biphasic affect fuel performance in the eld.
with the polar layer (glycerol/alcohol) being separated from the
biodiesel layer by settling or centrifugation followed by decanta- 2. Cold ow properties
tion. Many processes wash the separated biodiesel with water to
remove trace concentrations of glycerol, alcohol and catalyst. One disadvantage of biodiesel has to do with properties and
Many reviews [627] on biodiesel production by trans- performance of its main components (alkyl esters) when exposed
esterication have been published in the scientic literature. The to cold temperatures. Although eld studies on the effects of pro-
reaction is fast, inexpensive and high-yielding when using longed exposure to cold weather on biodiesel are scarce, there is
a homogeneous alkali catalyst such as sodium or potassium evidence that fatty acid methyl esters (FAME) from soybean oil
hydroxide or methoxide [28]. Classic reaction conditions are six (SME) develop problems when ambient temperatures approach 0
molar equivalents of alcohol (2:1 excess), 0.5 wt% catalyst with 2  C. This temperature range is generally higher than for conven-
respect to TAG, 60  C and 60 min conversion time [29]. Moisture tional petrodiesel fuels.
should be avoided with alkali catalyst because water can hydrolyze Diesel fuels generally develop start-up and operability problems
biodiesel resulting in the formation of free fatty acids or fatty acid when vehicles and fuel systems are subjected to cold temperatures.
esters of sodium or potassium (soaps). The nal composition of As ambient temperatures cool towards their crystallization
biodiesel depends on the fatty acid composition of its feedstock oil. temperature, high-molecular weight parafns (C18C30 n-alkanes)
 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489 483

Fig. 1. Schematic of generalized transesterication reaction mechanism for production of biodiesel from triacylglycerols (TAGs). R1, R2, R3 long-chain saturated or unsaturated
hydrocarbons; R4 alkyl group (CH3 methanol; C2H5 ethanol); DAG diacylglycerol; MAG monoacylglycerol.

in petrodiesel nucleate and form wax crystals suspended in a liquid Cold ow properties of biodiesel depend mainly on its compo-
phase composed of shorter-chain n-alkanes and aromatics [3034]. sition. Beef tallow contains 2537 wt% palmitic and 9.534.2%
Left unattended for a long period of time (such as overnight) the stearic acids mixed with unsaturated long-chain fatty acids [38].
solid wax crystals may plug or restrict ow through lters causing Conversion to tallow-FAME yields biodiesel that contains signi-
start-up and operability problems. cant quantities of methyl palmitate and stearate, FAME whose MPs
At low temperatures, higher-melting point (MP) components in are very high (27.8 and 37.0  C) compared with unsaturated methyl
the fuel nucleate and grow to form solid crystals. The temperature oleate (MP 20.7  C) [39]. As a result, CP and PP are relatively
where the crystals become visible and form a hazy or cloudy high (17 and 15  C) as shown in Table 2. On the other hand, SME is
suspension is dened as the cloud point (CP) [32,3436]. The CP of composed of 1518 wt% total methyl palmitate and stearate
biodiesel is generally higher than for petrodiesel, as shown for contents and has CP 0  C and PP 2  C. In contrast, CP and PP
several examples of FAME in Table 2, and the ASTM fuel standard D values reported for No. 2 petrodiesel are at much lower tempera-
6751 recommends it be taken into consideration when blending tures compared to most of the biodiesel fuels shown in Table 2.
[3]. Prolonged exposure of the fuel to temperatures at or below CP Neither CP nor PP efciently predicts how diesel fuels perform in
causes crystals to grow and form interlocking networks. Pour point tanks and fuel systems during cold weather [34,36,37]. Consequently,
(PP) of the fuel is dened as the lowest temperature where the fuel low-temperature lterability tests were developed that more effec-
ows or can be pumped [3437]. Both CP and PP should be closely tively predict limiting fuel temperatures where start-up or operability
monitored by the user to ensure trouble-free operation in cold problems may be expected after prolonged exposure. The rst test,
climates. cold lter-plugging point (CFPP), is accepted nearly worldwide and
maximum temperature ranges for this parameter are included in
European fuel standard EN 14214 [4]. However, this test does not
Table 2 correlate well with eld test data in North America. Although similar
Cold ow properties of biodiesel (FAME) made from various lipid feedstocks.
in procedure to CFPP, the less user-friendly low-temperature ow test
Feedstock lipid CP,  C PP,  C CFPP,  C LTFT,  C Reference (LTFT) was developed as a standard test for predicting operability of
Canola oil 3 4 4 [63] diesel fuels and fuel systems prevalent in North America. A complete
Corn oil 3 4 7 [64,65] examination of how CFPP and LTFT tests differ in terms of operation
Cottonseed oil 6 0 3 [47] and experimental conditions is presented in an earlier review [40].
Lard 11 12 8 [66]
Linseed oil 0 9 7 [67,68]
Summarizing, each test yields the lowest temperature where a spec-
Olive oil 2 3 6 [69] ied volume of fuel safely passes through a wire mesh lter under
Palm oil 14 14 12 [70] vacuum within 60 s. LTFT is more stringent in terms of conditions and
Poultry fat 4 6 1 [66] generally takes a longer time to complete than CFPP.
Rapeseed oil (<5 wt% erucic) 3 9 9 [71]
Similar to CP and PP, the performance of biodiesel in CFPP and
Soybean oil (SME) 0 2 2 0 [72]
Sunower seed oil 2 3 2 [69] LTFT tests depends mostly on its fatty acid composition. As shown
Tallow 17 15 9 20 [73] in Table 2, CFPP 2  C and LTFT 0  C were reported for SME. In
Used olive oil 2 6 9 [74] contrast, much higher values for CFPP and LTFT were reported for
Yellow grease 8 6 1 [63] tallow-FAME due to its higher total methyl palmitate and stearate
No. 1 petrodiesela 31 46 42 27 [72]
No. 2 petrodiesela 16 27 18 14 [72]
contents. Again for No. 2 petrodiesel, CFPPs are at much lower
(S < 500 ppm) temperatures than most of the biodiesel fuels shown in Table 2.
No. 2 petrodiesela 5 6 [75]
(S < 50 ppm)
3. Minor constituents and low-temperature performance
FAME fatty acid methyl ester; CP cloud point; PP pour point; CFPP cold
lter-plugging point; LTFT low-temperature ow test.
a
No. 1 and No. 2 petrodiesels are dened according to ASTM standard speci- Very small (trace) concentrations of minor constituents are
cation D 975 [76]. known to inuence low-temperature performance of biodiesel.
484 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489
These constituents are often referred to as contaminants, though
many of them originate either in the feedstock oil or may be
present following one of the production steps to convert the oil into
biodiesel. As discussed earlier, transesterication (Fig. 1) sequen-
tially converts the oil from TAG to DAG, DAG to MAG, and MAG to
glycerol with biodiesel being produced along the path. After
decantation, trace concentrations of glycerol are typically removed
during water washing and do not cause problems with operability.
However, residual MAG, DAG and TAG from incomplete conversion
are not soluble in water and may remain present in the nal
product biodiesel [41]. Furthermore, MAG may be the most abun-
dant compared with DAG and TAG, and saturated MAGs have a high
MP (77 and 82  C for monopalmitin and monostearin [42]).
Maximum limits are placed on free glycerol and total glycerol
(glycerol glycerol mass components in MAG, DAG and TAG)
content within ASTM fuel standard D 6751 (see Table 1). Based on
this calculation it is possible for biodiesel that is only 9697%
converted from feedstock TAG to meet the maximum limit (0.240
mass%) [41]. Other constituents that may be present in very small
concentrations following the conversion process include water, free
fatty acids, alcohol, sodium or potassium salts of fatty acids (soaps),
antioxidants, sterols and other unsaponiable matter.
Another class of constituents found to naturally occur in plant
oils is steryl glucosides. Sometimes confused with and referred to as
sterols in scientic literature, these compounds are glycosides
derived from a phytosterol and glucose as shown in the example
depicted in Fig. 2 for b-sitosteryl glucoside. They exist mostly in
acylated form (where R CmHnCO), which is very soluble in
vegetable oils. Depending on processing, total steryl glucoside
content may be higher in soybean oil than other plant oils [43].
Crude soybean and palm oils contain up to 2300 ppm steryl
glucoside while crude corn and sunower seed oils may contain
only 500 and 200 ppm steryl glucoside. Transesterication of the
parent oil also hydrolyzes the acylated steryl glucosides to the free
form (FStG) where R H [44]. Biodiesel made from crude soybean
oil was reported to contain 272 ppm FStG while biodiesel from
rened-bleached soybean oil contained 64 ppm FStG [45]. FStGs
possess a high MP (for example, 240  C for b-sitosteryl glucoside
[43]) and limited solubility in biodiesel or methanol. At concen-
trations as low as 1090 ppm, FStG may cause haziness in biodiesel
at room temperatures.
Processing before and after conversion to biodiesel may reduce
steryl glucosides content such that they pose no signicant prob-
lems. However, if residual FStGs are present at low concentrations,
then the likelihood they will settle at the bottom of storage tanks
increases [43]. Cold storage temperatures exacerbate the process
and may cause particles to act as seed crystals for forming larger
Fig. 2. Structure of b-sitosteryl glucoside. Source: Ref. [52].
agglomerates [41,43]. One hypothesis holds that FStG aggregates
form complexes with residual MAG and DAG amplifying precipi-
tation and settling of solid residues in biodiesel [41]. The presence
of moisture can complicate these problems because both MAG and
DAG are amphiphilic in nature and may interact with water. Finally,
blending with non-polar (hydrophobic) petrodiesel decreases
solubility which may accelerate precipitation. Regardless of origin,
large quantities of solid particles settling at the bottom of storage
tanks can restrict ow or clog lters in fuel dispensers and vehicles
after transfer at temperatures above CP of the fuel.
3.1. Analysis of acylglycerols and steryl glucosides
Bondioli et al. [46] analyzed the composition of white solid
insoluble residues formed during the production of both palm oil-
FAME and SME. Residues were collected from a washing centrifuge
used for the removal of glycerol during nal stages of water
washing. Analysis by Fourier transform-infrared (FT-IR) spectros-
copy and GCmass spectrometry (MS) identied the presence of
FStG composed of 6065 wt% b-sitosteryl glucoside and smaller
concentrations of campesteryl and stigmasteryl glucosides. Total
contents found in the biodiesel products were up to 160 and 38 mg/
kg in palm oil-FAME and SME, respectively. Analysis by FT-IR
detected no presence of MAG in the solid residues.
Van Hoed et al. [45] evaluated liquid and solid samples collected
from palm oil-FAME and SME storage tanks by nuclear magnetic
resonance (NMR) and GCMS. Turbid samples were distilled to
reduce FAME and concentrate the heavier constituents (MAG, DAG,
sterols, tocopherols and FStG). Analysis of hazy FAME samples
indicated trace concentrations of acylated steryl glucosides plus
FStG, MAG, DAG and free sterols where the maximum FStG content
was 300 ppm. Haziness in the biodiesel samples was observed at 25
and 60  C. Analysis of isolated solid precipitates by NMR showed
that they were composed of highly pure FStG. Solid residues
collected after ltration of biodiesel from storage tanks were
extracted sequentially by several organic solvents to separate
FAME, glycerol, MAG, DAG, sterols, acylated steryl glucoside and
FStG for analysis. Filtered SME residues were 1040 wt% FStG in
FAME with no signicant accumulations of MAG or DAG being
detected. It was concluded that FStG had the capacity to absorb up
to ten times their mass of FAME from the bulk solution. Unextracted
residues were 80 wt% FAME plus FStG and traces of MAG, DAG and
sterols. Analysis of puried FStG from lter residues by MS indi-
cated the presence of b-sitosteryl, campesteryl and stigmasteryl
moieties.
Contents of solid residues from commercial SME, cottonseed oil-
FAME and poultry fat-FAME and their blends with No. 2 ultra-low
sulfur petrodiesel (ULSD2; sulfur content  15 ppm) were analyzed
by GC and FT-IR spectroscopy [47]. Samples were blended at
20 vol% biodiesel (B20) in ULSD2 and chilled at 4  C for 24 h to
promote precipitate formation. After isolating the solids, FT-IR and
GC analyses revealed mainly FStG in precipitates from SME. In
contrast, precipitates from poultry fat-FAME were mainly
composed of saturated MAG monopalmitin and monostearin.
Cottonseed oil-FAME precipitates were composed of FStG and
saturated MAG.
A similar study [48] was conducted on insoluble matter isolated
after chilling SME, palm oil-FAME and yellow grease-FAME at 4  C
for 24 h. After reheating to room temperature, the total mass of
insoluble matter remaining in palm oil-FAME tended to increase
with blend ratio (vol% in ULSD2) up to 1000 ppm for B100. In
contrast, not more than 35 ppm total mass insoluble matter formed
in SME or yellow grease-FAME. A GC-method was devised for
separating and quantifying FStG, sterols, MAG, DAG and a-tocoph-
erol, though peaks for TAG and acylated steryl glucosides had
 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489 485

retention times too close to be resolved. GC and FT-IR analyses of

concentrated insoluble matter collected from neat (B100) SME
showed mainly the presence of FStG. In contrast to reports from the
studies by Bondioli et al. [46] and Van Hoed et al. [45] discussed
above, analysis of matter collected from palm oil-FAME indicated the
presence of saturated MAG monopalmitin and monostearin with no
detection of FStG relative to detection limits below 15 mg/kg.
Moreau et al. [49] developed a normal-phase isocratic high
performance liquid chromatography (HPLC) with evaporative light
scattering detection (ELSD) method to rapidly identify and quan-
titatively analyze FStG levels in precipitates from ltered
commercial biodiesel samples. Solid residues isolated from a turbid
SME sample were composed mainly of FStG and residual FAME
with no acylated steryl glucoside being detected. This method was
equally efcient with either ELSD or ultravioletvisible light
(UVvis) detection at wavelength 205 nm. MS analysis conrmed
that isolated FStG was composed of b-sitosteryl and campesteryl
glucoside chemical structures. The method was also applied to solid
lter cakes collected from biodiesel fuel lters.

3.2. Effects on cold ow properties

In the United States, fuel related problems with solid

precipitates plugging lters were reported for ferry boats fueled
by B20 blends crossing Puget Sound during the winter of
20042005. During the winter of 20052006, clogged diesel fuel
lters became a statewide problem shortly after a B2 mandate
went into effect in Minnesota. Analysis of CP and CFPP of bio-
diesel before blending indicated no lter-plugging potential.
Another case was reported in Utah when blending B100 down to
B20 caused a fallout of white slime near the bottom of storage
tanks that eventually found its way out to clog fuel dispenser
lters and enter customer vehicles [41]. Also during the winter of
20052006, eets in the eastern United States running on B20
blends experienced blocked lters [50]. Storage of the fuel blend
at 1.52  C caused formation of oc gels that disappeared upon
reheating to room temperature. GC analysis found that the solids
were composed mainly of saturated MAG and DAG with no
evidence of TAG or parafns present.
Photographs of fuel samples collected by a biodiesel fuel
distributor in Bloomington, IL in February 2006 are shown in Fig. 3.
Sample 96-1 on the left-hand side of Fig. 3(a) is an example of
clean SME with no visible solid residues forming. In contrast,
sample 96-6 is an example of SME that was stored in cold
temperatures for several days. This sample shows evidence of white
solid residues settling towards the bottom of the jar. After ltering
the separated solid residue was collected and is shown in the
sample vial in Fig. 3(b). GC analysis determined that this residue
was composed primarily of saturated MAG. The photograph in
Fig. 3(c) shows evidence of brown-colored solid residues settling
from a B50 blend of SME and No. 1 petrodiesel after several days of
storage in cold weather.
Reports of clogged fuel lters were generally attributed to the
formation of solid precipitates composed of saturated MAG or FStG
in biodiesel. As early as 1996, MAG and DAG were detected in
a creamy paste material recovered from plugged fuel lters in a bus
refueling station in Ames Iowa [51]. The buses were running on
a B20 biodiesel blend in No. 1 petrodiesel. Analysis of the paste
revealed 25 wt% MAG DAG where MAG was 95% saturated. Two
more recent studies [52,53] reported that solid residues collected
from plugged lters in Minnesota during the winters of 20052006
and 20062007 were mainly composed of saturated MAG. GC
analysis of solids formed in SME after cooling at 4.4  C for several
days indicated the presence of monopalmitin and monostearin at
mass ratios close to 2:1 plus traces of monoolein [53].
Fig. 3. Biodiesel samples collected by fuel distributor in Bloomington, IL, February
2006. Legends: (a) SME (soybean oil-fatty acid methyl esters; B100) samples, one clean
(#96-1) and one with white solid residues (#96-6); (b) isolated solid residues; (c) B50
blend of SME/No. 1 petrodiesel with light brown solid residues.
The potential for trace concentrations of minor constituents to
compromise cold ow properties and performance of biodiesel was
rst reported in 1996 [51]. That study concluded that adding
12 wt% unsaponiable matter in the form of a mixture mainly of
b-sitosterol plus a-tocopherol, squalane and squalene did not affect
CP, PP or DSC-measured completion of melt temperature of SME.
Based on DSC analyses, monopalmitin (C16) and monostearin (C18)
were soluble in concentrations of at least 0.25 and 0.2 wt%.
Although adding small concentrations of MAG and DAG did not
affect PP, CP increased when concentrations as low as 0.1 wt%
(1000 ppm) of each acylglycerol were added [51,54]. CP and
completion of melt temperatures increased signicantly when
monopalmitin or monostearin was present at concentrations
exceeding their solubility limit. Unsaturated monoolein (C18:1) did
not signicantly affect CP or PP. Unsaponiable matter did not
signicantly affect cold ow properties of a B20 SME/DF1 blend.
Allen et al. [55] reported that adding 1% canola oil (TAG) to
canola oil-FAME increases viscosity by 1.5%. Coconut oil-FAME
spiked with up to 5 wt% of a combination of MAG, DAG, FStG and
polar lipids increased viscosity by 5.8%. Pradhan and Shrestha [56]
developed empirical correlations for CP with respect to total glyc-
erol content in blends of SME, canola oil-FAME and ethyl esters
from soybean and canola oils in No. 2 petrodiesel. Although coef-
cients of regression were good (R2 0.93) for SME and soybean
oil-fatty acid ethyl esters, they were not as strong (0.78 and 0.53)
for blends with canola oil-fatty acid alkyl esters. Analysis of vari-
ance indicated that effects of moisture on CP were negligible for
concentrations up to 2700 ppm.
486 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489
Pfalzgraf et al. [52] determined the effects of trace concentrations
of MAG, FStG, water and soap and combinations of these constitu-
ents on CP of SME. FStGs were 99% puried from ltered SME
residues and the soaps consisted of a mixture of the sodium salts of
palmitic, stearic, oleic and linoleic acids. The CP of SME with nothing
added was 0.3  C. Results from a series of statistically designed
experiments showed that the maximum increase in CP was 3.6  C for
SME doped with 1 wt% MAG, 40 ppm FStG, 40 ppm soap and
500 ppm water. Individually, the most signicant effects on
increasing CP were caused by adding at least 0.6% MAG. The presence
of FStG did not greatly affect CP while soaps or water in combination
with MAG increased CP by as much as 3.3  C.
Selvidge et al. [53] determined that CP and CFPP were unreliable as
indicators of the highest temperature where precipitation of solid
saturated MAG from neat SME can occur. Biodiesel meeting the ASTM
D 6751 specication for total glycerol and having CP 0  C was found
to form white precipitates after storage at 9  C for several days. Similar
results were observed under the same conditions for B2.5 blends in
petrodiesel. White precipitates returned to translucent solution after
heating SME at 38  C. The CFPP of B2.5 blends of biodiesel from
different sources in No. 1 petrodiesel indicated no dependence on
increasing total glycerol, up to 0.3 wt% relative to B100. In contrast,
LTFT of blends increased with increasing total glycerol, suggesting
that the more stringent LTFT test conditions (slower cooling rate and
smaller lter pore size) are more effective for identifying problems
related to presence of saturated acylglycerols.
Two other studies [47,48] compared analysis of cold ow prop-
erties of biodiesel/ULSD2 blends with the tendency of these blends to
form solid residues while being stored at 4  C for 24 h. Results for
blends with SME, palm oil-FAME, cottonseed oil-FAME, poultry fat-
FAME and yellow grease-FAME showed that CFPP was very close to CP
at low blend ratios and tended to converge close to PP at higher blend
ratios. Blends with a higher tendency to form solid residues during
cold storage demonstrated CFPPPP convergence at blend ratios
between B10 and B20. This was the case for yellow grease-FAME,
cottonseed oil-FAME and one of two SME-based blends studied. In
contrast, palm oil-FAME, poultry fat-FAME and the second SME-based
blends showed a lower tendency to form solid crystals after cold
storage. This observation was offered to explain why these blends
showed CFPPPP convergence at higher (B50B70) blend ratios.
Van Hoed et al. [45] studied commercial biodiesel samples
demonstrating turbidity at 25 and 60  C. Results indicated higher
concentrations of FStG in commercial palm oil-FAME (57276 ppm)
compared with laboratory-prepared palm oil-FAME (62 ppm) or
chemically neutralized palm oil (<15 ppm). No correlation between
FStG concentration and degree of turbidity was observed suggest-
ing that concentration is one of several determining factors for
solid residue formation.
Moreau et al. [49] analyzed several commercial biodiesel
samples containing solid precipitates and solids isolated from
biodiesel at various points in the production and supply infra-
structure. Results for samples analyzed by normal-phase isocratic
HPLCELSD showed that FStG concentrations up to 68 wt% in bio-
diesel-derived solids, though one-third of these solids had less than
1% FStG. Only two samples, both isolated residues from B20 blends,
yielded high concentrations (6.87.4%) of MAG. One sample from
an in-plant transit pipe was composed of 21% FStG, 1.9% DAG, 1.4%
MAG and 1.6% free fatty acid in FAME suggesting that settling or
coating of solids within pipes employed to move nished biodiesel
may occur over extended periods.
4. Cold soak lterability
The numerous cases of clogged diesel fuel lters such as those
occurring in Minnesota during the winter of 20052006 imposed
a need to develop test methods for analyzing the potential of bio-
diesel to form solid precipitates after storage in cold temperatures.
In response, the biodiesel industry collaborated with ASTM to
improvise a specialized test to identify fuels that have potential to
clog lters [53]. The cold soak ltration test (CSFT) procedure is
currently published in Annex A1 of the biodiesel fuel specication D
6751 and, as of April 2009, as a standalone test method D 7501 [57].
The CSFT was developed by modifying ASTM method D 6217 for
Particulate Contamination in Middle Distillate Fuels by Laboratory
Filtration [52,53]. The test is bimodal and is not designed to
identify the chemical species causing the solid precipitation. To
fully meet specication D 6751, neat biodiesel (B100) must
demonstrate a maximum cold soak ltration time of 360 s (6 min) if
it is to be blended with petrodiesel and expected to satisfactorily
perform at fuel temperatures above 12  C. If the blends are
expected to perform at or below 12  C, then neat biodiesel must
demonstrate a maximum ltration time of 200 s [3].
The test procedure as outlined in Annex A1 of specication D
6751 was developed primarily for soy biodiesel (SME) [58]. The
method does not properly allow for biodiesel that solidies when
cooled at 4.5  C for 16 h before warming to the ltration temper-
ature (25  C). Changes to allow testing biodiesel from a wider range
in feedstocks were implemented in the recently published CSFT
method D 7501 [57]. Nevertheless, the CSFT is viewed by many
biodiesel producers as awed for several reasons [58]. First,
maximum time limits as specied in D 6751 were empirically set
based on the anecdotal evidence but have little scientic basis for
their selection. The test is not a real analytical test and demon-
strates poor reproducibility and repeatability. It takes up to 36 h to
complete, a period that is too long for many producers. Approaches
such as FT-IR, GC/MS or HPLC (discussed above) can analyze for the
presence of constituents that eventually form solid precipitates,
though they may be more costly and require some knowledge of
species to be identied. Essentially, the CSFT was viewed by many
as a compromise between cost and pragmatism in ensuring good
performance.
Before running the CSFT test, an important preparation step
must be taken if it cannot be conrmed the biodiesel was not
exposed to temperatures below 20  C before acquisition. This step
removes the thermal history of a designated sample by (1) heating
at 40  C under inert atmosphere for at least 3 h to dissolve any
solids that may have already formed; (2) allowing it to sit for 24 h at
20 C (preferably in a water bath); (3) shaking vigorously for at
least 60 s and transferring to a clean container. After sample
preparation, 300 mL of biodiesel is put into a sealed 500 mL glass
bottle and cooled at 4.5  C for 16 h. After the cold soak is completed,
the sample is removed and warmed in a water bath for 2 h (4 h if
solidication occurs) with no agitation. Immediately after its
removal from the water bath, the sample is gently swirled then
ltered through a 0.7 mm glass ber lter under 2125 in Hg (71
85 kPa) vacuum. CSFT time is recorded as the time (s) necessary for
the entire sample to pass through the lter [3,57].
Selvidge et al. [53], applying an early version of the CSFT where
a 1.6 mm pore size lter was used, reported elevated ltration times
after saturated MAG formed solid precipitates in SME. Most
samples with less than 0.24 wt% total glycerol had ltration times
below 250 s. As discussed earlier, increasing total glycerol in blends
of SME in No. 1 petrodiesel blends elevated LTFT and had no
signicant effect on CFPP. It was concluded that slow cooling rates
and relatively tight lter pore sizes were preferred conditions for
developing a ltration based performance test.
Pfalzgraf et al. [52] studied the effects of adding saturated MAG,
FStG, soaps and water on cold soak lterability of SME. The FStG
(99%) was isolated from commercial biodiesel and soaps were
a mixture of sodium salts of fatty acids (palmitate, stearate, oleate,
 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489
linoleate). The method was performed with cold soaked SME
samples being warmed for 2.5 h before ltering through a 0.7 mm
pore size glass lter under 78 kPa vacuum. Filtration time was 88 s
for SME with nothing added. For spiked samples, ltration time was
more sensitive than CP (discussed earlier) to the presence of FStG
and soaps as only 10 ppm of either constituent increased time
comparable to the addition of 0.30.4 wt% (30004000 ppm)
saturated MAG. Interactions between the added compounds
strongly affected ltration time and adding 1 wt% MAG 40 ppm
FStG 40 ppm soaps 500 ppm water caused the maximum
increase to 3562 s. Presence of water increased ltration time when
either MAGs or FStGs were present; however, water decreased
ltration time when at least 20 ppm soaps were present. Elevated
times were also observed for samples containing FStG or soaps that
were not cold soaked.
Tang et al. [47] investigated the rates of solid precipitation in
SME, cottonseed oil-FAME and poultry fat-FAME by soaking them
and their blends in ULSD2 for 24 h at 4 and 23  C. Filtration was
conducted under 68 kPa vacuum. The SME blends soaked at 23  C
demonstrated ltration times below 300 s with time increasing
slightly with increasing blend ratio. In contrast, soaking at 4  C
signicantly increased ltration time for B5B70 blends compared
to neat SME (240 s) and ULSD2 (120 s). A maximum ltration time
of 2280 s was observed for a B50 blend. In addition, total precipitate
masses were signicantly higher for B10B70 blends than for neat
SME or ULSD2. Decreases in ltration time as blend ratio increased
in excess of B70 were attributed to increases in solubility of solid
residues relative to decreases in ULSD2 in the blends. A minimum
storage time of 20 h at 4  C was necessary for total precipitate mass
concentration in neat SME to exceed 10 ppm. Neat SME also
demonstrated a signicantly higher rate of precipitate formation
than cottonseed oil-FAME or poultry fat-FAME, and this was
attributed to the presence of FStG (discussed above). Soaking
poultry fat-FAME blends in ULSD2 at 4  C resulted in <5 ppm total
mass solid precipitates at all blend ratios. Similar tests with
cottonseed oil-FAME resulted in <20 ppm total solid precipitate
formation with <7 ppm for blend ratios up to B70.
A companion study [48] examined the effects of soaking SME,
palm oil-FAME and yellow grease-FAME and their blends with
ULSD2. Test conditions were the same as in the rst study [48]. This
time, soaking SME blends at 4  C yielded no signicant increase in
ltration time relative to soaking at 23  C [48]. This observation was
attributed to SME for the second study being acquired from
a different supplier and being more resistant to large solid
precipitate formation. As noted earlier, solid residues collected
from SME and its blends were composed mainly of FStG. Although
total mass of precipitates did not exceed 25 ppm at all blend ratios,
residues collected from B20 blends were greater in mass than those
from neat SME or ULSD2. This trend was consistent with results for
SME blends in the rst study. The B70B100 yellow grease-FAME
blends exhibited signicant increases in ltration time when
soaked at 4  C relative to results for blends soaked at 23  C.
However, ltration times were less than 300 s for blend ratios up to
B70 and total precipitate mass was <35 ppm for all blends. Finally,
CSFT increased with increasing blend ratio in palm oil-FAME blends
soaked at both temperatures, though ltration times were signi-
cantly greater for blends with ratios above B50 soaked at 4  C. Solid
precipitates from neat palm oil-FAME were in the form of white
wax crystals with total mass concentration was 1000 ppm and
decreasing linearly with respect to decreasing blend ratio. The
composition of the crystals was monopalmitin and monostearin
(discussed above).
Lee et al. [43] applied ASTM method D 2068 [lter-plugging
tendency of distillate fuel oils] to study the role of dispersed solid
FStG precipitates in lter blocking. This test was developed for fuels
487
whose end use demanded an exceptional degree of cleanliness and
is applicable to fuels with kinematic viscosity 1.56.0 mm2/s at
40  C [35,59]. Filter-plugging tendency (FPT) is measured by
passing 300 mL of fuel at 20 mL/min through a 1.6 mm glass ber
lter and monitoring pressure drop across the lter. FPT is calcu-
lated from an empirical correlation based on maximum pressure
drop observed during passage through the lter. Evaluation of
a commercial SME sample containing 68 ppm FStG resulted in
FPT 15.03 (the maximum value) at 25  C. Decreasing FStG content
in SME decreased FPT such that SME containing 22 ppm FStG
yielded a passing score of FPT 1.03. Results for FAME made from
ve vegetable oils and fats suggested that the FPT test was more
sensitive to variances in solid precipitate formation than an earlier
version of the cold soak ltration test method employing a 1.6 mm
pore size glass ber lter [60].
5. Removing solid precipitates
Biodiesel fuel producers are making adjustments to ensure their
products will pass the CSFT. Factors include choice and quality of
lipid feedstocks and the robustness of the process and its associated
purication steps [58]. High-vacuum distillation is an easy process
modication but comes at increased cost. Distillation may not be
necessary if the process stream is cooled and ltered as it leaves the
facility.
Inventions for separating and removing solid precipitates from
commercial biodiesel were patented. These inventions feature the
employment of ltering aids, absorbents or chemical agents
designed to be integrated into existing biodiesel production
processes. One application decreases FPT by chilling biodiesel at
4.421  C for selective removal of FStG after production [60,61]. The
invention employs a combination of preparatory steps including (1)
diatomaceous earth mixed in a slurry with biodiesel or directly in
the lter bed; (2) magnesium silicate mixed in a slurry; (3)
replacing the water washing step in the biodiesel production
process by mixing with 1.52 wt% silica hydrogel under heat and
negative pressure (vacuum); and (4) adding deoiled lecithin and
subjecting the mixture to a degumming procedure. Each step is
followed by controlled ltration to remove solid precipitates. This
invention was shown to signicantly reduce FStG levels without
affecting MAG, DAG or TAG concentrations.
A second application decreases CSFT by removing solid precip-
itates after biodiesel production [62]. The cold ltration step
involves cooling biodiesel to 21  C, mixing with diatomaceous earth
to form a slurry and ltering the mixture through a pressure leaf
lter followed by a polishing lter to remove any remaining sedi-
ments or diatomaceous earth. Another process, referred to as the
Green Tea FASTRACK process (patent pending) utilizes three steps
to remove constituents that can cause biodiesel to fail the CSFT [58].
This process utilizes a proprietary mixture of materials that
chemically react with constituents followed by absorption and
ltration.
6. Concluding remarks
Commodity plant oils remain the predominant source for
obtaining biodiesel by transesterication with methanol or ethanol.
The majority of these oils contain small concentrations of steryl
glucosides that transform into insoluble FStG as they are converted
into biodiesel. Trace quantities of unconverted partial acylglycerols,
particularly MAG, may also remain in the nal biodiesel product.
Recent experiences revealed these constituents may cause fuel
quality issues if the biodiesel is stored for extended periods in cold
temperatures. Aggregation and growth of solid residues were
observed to occur in fuels that were within ASTM D 6751
488 R.O. Dunn / Progress in Energy and Combustion Science 35 (2009) 481489
specications (Table 1). Formation and settling of solid precipitates
at the bottom of storage tanks caused plugged lters in fuel
dispensers and vehicles.
Industry standard test methods for evaluating cold ow
performance such as CP and CFPP do not predict the propensity for
biodiesel blends to form solid precipitates caused by presence of
minor constituents when stored in cold weather. Cold ow prop-
erties of biodiesel are mainly affected by fatty acid mono-alkyl ester
composition and are not sensitive to the effects of long-term solid
residue formation caused by trace concentrations of MAG or FStG.
Concerns for maintaining good fuel quality while storing bio-
diesel in cold temperatures led to the development of the cold soak
ltration test (CSFT) for predicting the potential of a biodiesel fuel
to form solids. This outcome was analogous to the earlier drive to
develop an induction period test to monitor oxidative degradation
of fuel quality that is now part of both the European and United
States (ASTM) biodiesel fuel standards. Thus, maintaining fuel
quality year-round is becoming more of an imperative for the
biodiesel industry as commercial markets continue to grow in the
United States.
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