Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

SAE TECHNICAL
PAPER SERIES

Winterized Methyl Esters from Soybean Oil:

An Alternative Diesel Fuel With Improved
Low-Temperature Flow Properties

Robert 0.Dunn, Michael W. Shockley and Marvin 0.Bagby

Oil Chemical Research, USDA, ARS, NCAUR

Reprinted from: State of Alternative Fuel Technologies 1997 -

(SP-1274)

MAY 0 8 E997

International Spring Fuels

(PIm The Engineering Society
For Advancing Mobility & Lubricants Meeting
and sea Air and Space. Dearborn, Michigan
I N T E R N A T I O N A L Mav 5-8.1997
-

400 Commonwealth Drive, Warrendale, PA 15096-0001 U.S.A. Tel: (412)776-4841 Fax:(412)776-5760

 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

isgivenonthecondiffionhowever,thatthecopierpaya$7.00perarticlecopyfeethrough
theCoowiahtClearanceCenter. Inc. OoerationsCenter.222 RosewwdDrive.Danvers.
.. - . .. "
Law. Thiswnsentdoesnotextendtootherkiidsofcopyingsuchaswpyingforgeneral
di~bution,foradvertisingorpromotio~Ipurposes,forcreatingnewcollectivewo~or
forresale.

SAE routinely stocks printed papers for a period of three years following date
ofpublication. DirectyouronleffitoSAECustornerSalesandSatisfactionDepartment.

Quantity reprintratescanbeobtainedfrmtheCustmerSales andSatisfactionDepart-

ment

TorequestpermissiontoreprintatechnicalpaperorpermissiontousewpyrightedSAE
publicationsinotherwolks, contactthe SAE PublicationsGroup.

GG
M013IUW L?ATA&45E
All SAE oa~em,standards. and selected

Nopartofthispublicationmayby~roducedinanyfon,inandedronicretrievalsystern
orothennrise, withoutthepriorwrittenpermissionofthepublisher.

lSSN01487141
CopyrigM1997SocietyofAutomotiveEngineers, Inc.

de
available by which discussionskill printedwith the paper if it i5 &blished in SAE
Transactions. For permissionto publishthis paper in full or in part, contact the SAE
PuMicatiwrsGroup.

Persoffiwishingtosubmitpaperstobe~~l~ideredforp~ConorptM'~onthrough
SAE should sendthemanuscriptora 3M)wordabstractofapropcsedrnanuscriptto:
Secretary, EngineeringMeetingsBoard,SAE.

Printedin USA
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018
Winterized Methyl Esters from Soybean Oil:
An Alternative Diesel Fuel With Improved
Low-Temperature Flow Properties
Robert 0. Dunn, Michael W. Shockley and Marvin 0. Bagby
Copyright 1997 Society of Automotive Engineers, lnc
ABSTRACT
Methyl esters from vegetable oils (biodiesel) are very
attractive as alternative fuels for combustion in direct injection
compression-ignition (diesel) engines. Biodiesel fuels have low-
temperature flow properties that limit utilization during cooler
weather in moderate temperature climates. Although
winterization reduces the cloud point (CP) of methyl soyate from
0 to -2O0C, liquid product yields were relatively low (0.30-
0.33 gig). Winterization of methyl soyate-cold flow improver
mixtures decreased CP by -1 1°C and increased yields to 0.80-
0.87 gig. Winterization of methyl soyate from hexane and
isopropanol solvents gave similar results. Differential scanning
calorimetry (DSC) analyses showed that nucleation mechanisms
of methyl esters were significantly affected by winterization.
INTRODUCTION
Methyl esters from vegetable oils have many
characteristicsthat make them attractive as a fuel for combustion
in direct injection compression-ignition (diesel) engines (1).
With respect to distillate fuels, combustion of methyl esters is
known to reduce smoke, hydrocarbons and polyaromatic
hydrocarbons emissions and slightly reduce carbon monoxide
emissions while delivering comparable engine
performance (2-5). Methyl esters are generally safer to store and
handle due to high flash points and an environmentally
innocuous nature. As a fuel, methyl esters from vegetable oils
provide a positive energy balance of at least 2:l (2).
Field demonstrations with methyl soyate (SME, from
'ansesterification of soybean oil with methanol) has shown that
start-up and operability problems tend to develop when
overnight ambient temperatures approach O°C. This limit agrees
well with those predicted in bench-scale low-temperature flow
test (LTFT) studies (6). Given that the analogous limitation for
No. 2 diesel fuel is -14OC, it follows that the cold flow properties
of methyl esters from vegetable oil will preclude widespread
commercialization as fuels and fuel extenders in moderate
temperature climates such as those in North America.
One recent repon (6) showed that a linear correlation exists
between operability limit and cloud point (CP) for fuel
formulations with 10-100 vol% SME in distillate fuels. That is,
Oil Chemical Research, USDA, ARS, NCAUR
both cold filter plugging point (CFPP) and LTFT are directly
proportional to CP. Other studies (7,8) confirmed that diesel
fuel flow improvers significantly reduce pour point (PP) of
blends as well as neat methyl esters. These studies also showed
that additives do not greatly affect filterability or CP of blends
and that additives destroy the linear correlation for neat methyl
esters. Overall, these studies suggested that approaches for
improving cold flow properties of methyl ester fuels and
extenders should be selected initially on the basis of potential to
reduce CP.
Winterization is a popular technique for reducing high
melting point (P-crystal form) of vegetable oils to facilitate
easier handling and pouring of salad oils and dressings (9,lO).
This technique requires refrigeration ofthe oil over a prescribed
time period then drawing the liquid portion off separately.
Removal of partially solidified triglycerides reduces the CP and
PP of the product liquid. Given the nature of methyl esters such
as SME, it follows that winterization may be useful in decreasing
CP by decreasing the total concentration of saturated
components. One preliminary study (8) showed that the CP of
SME may be decreased to -16'C. Another study (1 I) showed
that crystallization onset temperature of the high melt region
may be reduced by 10°C. Both studies showedthat winterization
of neat SME required a step-by-step processing due to a
relatively narrow difference between CP and PP of SME
(typically 2-3°C). Both studies also showed that winterization of
neat SME gave liquid product yields less than 0.30 gig. These
relatively low yields were attributable to rapid agglomeration of
saturated methyl ester crystals leading to occlusion or trapping
of unsaturated methyl esters within pockets formed when solid
crystals agglomerate during cooling.
Low-temperature fractional ctystallization from organic
solvents is useful in preparation of pure fatly compounds and in
the production of higher quality salad oils (9,12). Hexane, a
solvent frequently employed in extraction of oils from oilseeds,
and isopropanol are useful in this regard. Although for food
applications solvent fractionation demands expensive solvent
removal equipment, requirements for improving cold flow
properties of "fuel-grade" methyl esters may be more cost
effective.
The present work is a study of winterization-based
fractionation techniques with the goals of increasing liquid
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018
product yield and decreasing process time. Modifications
include the addition of PP depressants to both winterization of
neat methyl esters and methyl ester-solvent mixtures. Liquid
products are compared on the basis of their overall yield, gas
chromatography (GC) analysis of saturated and unsaturated
components and low-temperature flow property measurements.
Stressing the necessity for screening approaches and owing to
the well established linear correlation between filterability and
CP, low-temperature flow properties are evaluated by
comparing CP data. Finally, heating and cooling differential
scanning calorimetry (DSC) curves are analyzed to determine
effects of various winterization methodologies on nucleation and
crystallization of SME in the high melting point (p-form) region.
MATERIALS AND METHODS
Methyl soyate (SME) was from lnterchem Environmental
(Overland Park, KS) via the National Biodiesel Board (Jefferson
City, MO). Samples were double-vacuum distilled at the
refinery to remove nearly all traces of glycerol. Capillary GC
analysis showed 14.7 wt% hexadecanoate (C16), 5.0 %
octadecanoate (CIS), 26.2 % 9Z-octadecenoate (CI 8: I), 44.4 %
9Z,12Z-octadecadienoate (ClS:2) and 9.6 % 9Z,12Z,15Z-
octadecatrienoate(C18:3). Other physical properties have been
reported elsewhere (6). Winterfow, a mixture of light aromatic
and heavy petroleum naphtha, trimethyl benzene isomers,
propylene glycol ether, xylene, hydroxyethylated amino-
ethylamide, cumene and ethyl benzene, was from Starreon Corp.
(Englewood, CO); DFI-200, a mixture of severely hydrotreated
light naphthenic distillates and ethylenelvinyl acetate
copo!ymers, was from Du Pont (Wilmington, DE). lsopropanol
(99.9 %) and HPLC-grade hexane were from Fisher Scientific
(Pittsburgh, PA).
Winterization studies were carried out by placing mixtures
in Erlenmeyer flasks, covering with aluminum foil and
immersing them in a Neslab (Portsmouth, NH) RTE-140
refrigerated bath. For neat SME and SME-additive mixtures,
bath temperature (T,) was set initially at 0°C (k0.2') and the
mixtures equilibrated overnight. For SME-solvent mixtures, T,
was estimated by first measuring CP of the unfractionated
mixture; equilibration time depended upon observed rate of
crystallization. Solutions were manually stirred in 15 min
intervals unless overnight equilibration was required. Solids
were removed by filtration through a porcelain Biichner funnel
(8.0 cm ID) fitted with a Whatman (Maidstone, England) No. 1
filter paper (7.0 cm OD). The Biichner funnel was stored in a
freezer prior to filhation to reduce melting of solids hack into the
liquid portion during filhation. Filtration with house vacuum
generally took less than 30 s. For neat SME and SME-additive
mixtures, liquid fractions were step-by-step winterized by
reducing T, in 2°C increments and repeating the equilibration
and filtration steps until liquid immersed at -10°C displayed no
observable clouding for a minimum of 3 h.
Equipment and methods for determining CP and PP in
accordance with American Society for Testing and Materials
(ASTM) standards have been described elsewhere (6). Product
yields were determined following removal of organic solvent, if
present, by in vacuo rotary evaporation for 30 min. Fatty acid
compositions of methyl ester mixtures were determined with a
Perkin Elmer (Norwalk, CT) Autosystem GC with a
25 m x 0.32 mm ID BPX7O column from SGE (Austin, TX).
Samples were diluted in acetone to facilitate analysis of residual
solvent. Samples (1 pL) were injected into He carrier gas
(1 mllmin) and analyzed with the following temperature
program: hold at 50°C for 5 min, ramp at lOo1minto 250°C, hold
at 250°C for 10 min. Prior to GC analysis, samples containing
cold flow improver ( Winterfow or DFI-200) were pre-treated
for separation of polymeric compounds. This was done by
filtering 100 mg of sample through a column packed with 200-
400 mesh silica gel from Aldrich (Milwaukee, WI) and rinsing
with25 mL hexane eluent. Hexane was subsequently removed
by in vacuo rotary evaporation.
Differential scanning calorimetry (DSC) was conducted
with a TA Instruments (New Castle, DE) DSC 2910 and
TA 2 100 personal computer-based controller. The measurement
cell was purged with low-pressure N2 gas; sub-ambient operation
was facilitated by a heat exchanger with liquid N, coolant on the
DSC cell. For each scan, 8-12 mg of sample was hermetically
sealed in an aluminum pan and tested against an empty pan. For
heating scans, samples were rapidly cooled and held
isothermally at -lOO°C for 10 min then heated at S0/min to 40°C;
for cooling scans, samples were equilibrated at 40°C then cooled
at 5"Imin to -lOO°C. Heating curves were analyzed to infer
completion-of-melt type onset temperature (T,). Procedures for
determining T, have been outlined elsewhere (7). Cooling
curves were analyzed to infer crystallization onset temperature
(T2)utilizing procedures outlined by Heino (13). Essentially, T,
and T2 were determined as points at the intersection of lines
extrapolated from @-form peaks and their corresponding
baselines about the solid-liquid transition. Onset temperatures
reported in this work are mean values of measurements from a
minimum of three replicate analyses, each with "fresh" samples.
RESULTS AND DISCUSSION
As discussed above, at least two earlier studies examined
winterization as a means for improving the cold flow properties
of neat methyl esters from vegetable oils. Very low yields
showed that removal of saturated components in SME led to
significant losses in unsaturated components. This work
examines several methods for modifying the physical chemistry
to reduce the rate of occlusion or adsorption of unsaturated
methyl esters within crystals to increase yields of SME-product
with improved low-temperature flow properties.
Previous work (8) has demonstrated the effectiveness of
Winterflow and DFI-200 as additives for reducing PP of SME.
These additives were shown to alter the habit and growth of
solid crystals as temperatures decrease below the CP of the
mixture (8,14,15). It is likely these additives reduce PP by
slowing growth and agglomeration of predominantly saturated
methyl ester crystals. Hypothetically, reducing growth and
agglomeration of crystals should result in decreasing the rate of
occlusion of unsaturated methyl ester molecules from bulk
liquid, allowing separation of liquid product with higher yields
and total unsaturated methyl ester contents. Similarly,
winterization of methyl esters from organic solvent may
beneficially alter diffusion in the bulk liquid and reduce
occlusion. A third variation combines the first two by adding
cold flow improvers to the solvent-SME mixtures.
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018
Table 1. GC analyses of fatty acid composition of step-by-step winterized methyl soyate (SME).
I I
None (Trial 1)
Winterflow
tinw~nr~.rized
SME 11.7
I,, - bath irmpcraturr: L -mas, fra:taon ot liquid produ;~ Cl6 = hcxaJr;~noatr. C18 :: acradecanusts. ('18 1 - 9%-ocl;rdi.uenoale.
*Polvmer additives removed bv adsomtion onto ~. o l a rohase
. silica eel orior to GC analysis
'liqutl~braliunlime = 16 h slcp (ovcrn~ght)
:L = (n~assd f IlquiJ c~II~ctcd)/(lolaI
INS ulnlrri7ed during rtcp,
'No measureablc precipitation ofsolids.
The remainder of this work employs the term "winterized
neat SME" in reference to products from winterization without
solvent or additive and the term "winterized SME-additive
mixtures" in reference to products from winterization of SME-
additive mixtures without solvent. The term "solvent-based
winterization" refers to winterization of either neat SME or
SME-additive mixtures from hexane or isopropanol solvent.
LIQUID PRODUCT YIELDS AND METHYL ESTER
COMPOSITIONS. Step-product liquid yields (gig) from
winterization of neat SME and SME-additive mixtures are listed
in Table 1. Winterization of SME-additive mixtures consistently
increases liquid product yield with respect to neat SME at the
same step. Winterization of neat SME produced a maximum
solid (or minimum liquid) step-yield at T, = -2°C. Winterization
of SME-additive mixtures produced maximum solid step-y ields
at T, = -4" for Winierflow and -6'C for DFI-200. Also, only I -
3 % of starting material was removed in the step(s) prior to the
maximum solid yielding step. Thus, similar liquid product
yields might be obtained in reduced process time if winterization
of SME-additive mixtures was initiated at lower T,-values.
Nevertheless, winterization of SME-additive mixtures
significantly reduced the total mass of solids removed, allowing
a significant increase in final liquid product yields (Table 2),
with respect to winterization of neat SME under similar
135
Methyl Ester Fatty Acid Group" (gI100 g) I
C18:2 / C18:3 1 Other
50 26.2 43.4 9.6 i O .1
conditions.
Step-product methyl ester compositions for winterized neat
SME are also listed in Table I (compositions for untreated SME
are listed for comparison). As expected, each progressing step
in the process showed gradual decreases in saturated methyl
hexadecanoate ((216) and octadecanoate (CIS) concentrations
and complementaly increases in unsaturated methyl 9Z-
octadecenoate (C 18:I), 9Z, 12Z-octadecadienoate (C18:2) and
9Z,12Z,15Z-octadecatrienoate(C18:3) concentrations, with
respect to winterization without additives. Final liquid product
compositions plotted in Figure 1 show that incorporation of cold
flow improvers reduced the efficacy of winterization by
increasing saturated methyl ester concentrations and decreasing
unsaturated methyl ester concentrations. One notable exception
to this trend was C18:2, where the presence of additives boosted
its concentration in the final product by more than 5 g1100g.
Total saturated and unsaturated methyl ester compositions
for winterized neat SME and winterized SME-additive mixtures
are given in Table 2. Winterization of SME-additive mixtures
resulted in slight increases in total saturates relative to
winterization of neat SME. lnspite of this apparent reduced
effectiveness, it is likely that the additives were effective in
hindering the rate of occlusion of unsaturated methyl esters from
solution. For example, winterization of SME- Winterflow yielded
87.00 g of liquid product (from I00 g of starting material) with
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

Table 2. Yields and total saturated and unsaturated fatty acid methyl ester compositions of winterized liquid
products. Additive loading = 2000 ppm

Winterized Fraction SMEIS" Steps th T,h L' Total Total

(PIS) (h) ("C) (gig) Saturates Unsaturates
(gi100g) (gi100g)

SME in Isopropanol 0.2282 1 3.5 -15 0.8604 10.8 86.6

SME- Winterflow in Isopropanol 0.1979 I 16 -15 1.011 13.5 86.5

0.1989 I 4 -20 0.9890 13.3 86.7

I SME- DFI-ZOOin lsopropanol 0.1996 0.9962'

SME in Hexane

See Table 1 for abbreviations.

"Methyl soyate/solvent (S) mass ratio.
"or final step.
'Weight following 30 min in vacuo rotary evaporation of solvent (if present).
dProduct liquid contained 11.9 d l 0 0 g residual solvent.

9.3 g/100 g of total saturates. Data in Table 1 show that
winterization of neat SME yielded only 44.51 g/100 g when total
saturates were reduced to 9.6 g/100 g. Furthermore, mass
balances showed that very little of the C18:l and C18:2 methyl
esters, and less than half of the C18:3 methyl esters, were
removed during winterization. These results indicate that cold
flow improvers reduced growth and agglomeration of saturated
methyl ester crystals after they form in the cooled solution.
Consequently, the rate of occlusion of unsaturated methyl ester
molecules within solid crystal agglomerates also decreased
during winterization. Reduction in occlusion resulted in
filtration of crystals with generally higher total saturates
concentration. It is also likely that additives reduced the average
particle size of crystals allowing smaller crystals to filter through
and remain in the liquid product. This may account for the
increase in total saturates concentration in winterized SME-
additive mixtures with respect to winterized neat SME. It also
explains why liquid product yields were higher for winterized
SME-additive mixtures.
Final product yields and total saturated and unsaturated
methyl ester compositions for solvent-winterized SME and
SME-additive mixtures are also listed in Table 2. These data
show that winterization yields from solvent-based mixtures were
also superior with respect to winterization of neat SME. In
addition, they demonstrate that cold flow improvers can
increase yields from solvent-winterization, with respect to
solvent-winterization of neat SME. Yields were calculated on
the basis of mass obtained following separation of solvent, if
present, by in vacuo rotary evaporation. Some yields were
inflated by residual solvent (obvious examples include SME-
Winterflow in isopropanol at -15'C and in hexane at -34.5'C).
However, solid yields agreed with observations concerning
effects of cold flow improvers and solvents on winterization of
SME. Under the conditions of these studies, solvent-based
winterization was capable of reducing saturates by 30-50 wt%
relative to total saturates in SME in one step, generally with
process times less than 6 h. In general, the presence of cold flow
improvers required reduction in T, to produce timely
winterization.
Finally, it is worth noting that obtaining accurate analyses
of fatty acid compositions of various SME-additive mixtures was
complicated by the need to remove the polymer additives via
preparatory column-separation prior to injection into the GC.
During analysis there was some retention of esters on the
stationary phase of the preparatory column where unsaturated
esters demonstrated a particular affinity. Although large sample
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018
60
Wintetiled SME, Final Product
50
40
-
30
20
cis Ci8
F a W Aoid Group
No Additives
Figure 1. Effect of winterization on fany acid composition of SME. See Table 1 for abbreviations.
quantities (- 100 mg) tended to ameliorate those effects, the data
presented in this work may reflect slightly inflated saturated or
reduced unsaturated methyl ester concentrations.
LOW-TEMPERATURE PROPERTIES. Table 3 is a list
of CP and PP data obtained for winterized products UI Table 2.
Data for unwinterizeed neat SME and sM~-additivemixtures
are listed for comparison. In general, CP data for solvent-
winterized products were comparable to those for winterized
neat SME-additives mixtures. Addition of cold flow improvers
generally reduces the effects of winterization and solvent-based
winterization on improving CP, with respect to TB and
equilibrationtime.
It is notable that CP data of winterized SME-additive
mixtures were very close to TBin the fmal step (CP = -1 1°C;
TB= -lO°C). In other words, the liquid-solid phase equilibrium
was very stable prior to filtration. This result also means that re-
melting of solids back into liquid solution during filtration was
not significant. In this respect, the presence of cold flow
improvers increased cool-temperature filtration efficiency.
Solvent-winterized products did not show an analogous
trend between TBand CP. This was not unexpected because the
TB-value necessary to produce timely equilibration (r; 6 h)
decreased with respect to the suitability for a solvent to dissolve
SME solutes. Hexane being more effective as a solvent required
a lower TB(-25 to -30°C) than isopropanol (-15'C) to produce
timely winterization. Nevertheless, under conditions of these
studies solvent-based winterization of neat SME gave CP and
product yields comparable to those from winterization of SME-
additive mixtures and in substantially less time. Lee et al. (1 1)
137
C18:i Cik2 Ci8:3
DFI.200
also studied hexane-winterization of SME and reported similar
results.
Solvent-based winterization of SME-additive mixtures
showed generally increased yields and decreased effects on CP
than solvent-winterized neat SME products. These results were
analogous to those discussed with respect to effects of
winterization on unsaturated methyl ester concentrations.
Figure 2 is a plot of CP as a function of total saturate
concentration in methyl ester mixtures. The line drawn through
the data corresponds to the following equation:
CP = 1.4403 *(Total Saturates) - 24.8 (1)
where the regression coefficient (RZ) was 0.7906 and variance
from residuals (02)was 5.5762. Equation (1) shows that CP is
nearly a linear function of total saturated methyl ester
concentration. Earlier studies (discussed above) demonstrated
a direct linear relationship between CP and low-temperature
filtration limits (LTFT and CFPP). Equation (1) shows that a
direct linear relationship between total saturates concentration
and low-temperature filtration limits is also very likely to exist.
Above it was noted that the presence of cold flow
improvers reduced occlusion of unsaturated methyl esters by
hmdering growth and agglomeration of saturated methyl ester
crystals. Similar results were noted for solvent-winterized
mixtures. The reduction in average crystalline particle size led
to an areduction in retention of saturated methyl esters, relative
to winterization of neat SME. The results in Fig. 2 show that
increasing total saturates concentrationof a methyl ester mixture
directly influences CP. As a result, a trade-off exists where
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

Table 3. Low-temperature properties and differential scanning calorimetry (DSC) heating curve
onset temperatures of winterized liquid products. Additive loading = 2000 ppm.

Winterized Fraction TB~ CP6 PP T,d Predicted C P

PC) PC) PC) PC) ("C)
SME (Trial 1) -10 -20.0 -21.0 9.6 3.9
SME (Trial 2) -10 -- -- 10.1 4.7
SME- Winterflow -10 -11.3 -- 5.6 -1.9
SME- DFI-200 -10 -11.3 -- 8.6 2.5

I SME in ~sopropanol 1 -15 1 -8.7 / -9.0 1 9.1 1 3.2 1

ISME- Winterflow in Isopropanol
1 -15
-20 / -3.7
-53 1 -9.0
-- 1 7.7
6.8 / 1.2
-0.2 I
ISME-DFI-200 in Isopropanol

SME in Hexane -25 -10.3 -11.3 9.1 3.2

-30 -10.3 -11.0 10.1 4.7
SME- Winterflowin Hexane -34.5 -7.3 -12.0 5.1 -2.6

I SME-DFMOO in Hexane 1 -34 1 -5.0 1 -12.0 1 5.3 1 -2.3 1

abbreviations.
%r final step.
bMeanvalues (n = 3);variances i 1.3333.
<Meanvalues (n = 3); variances s 4.3333.
Wean values (n = 3, minimum); variances =0.0196-10.3684.
'Calculated from Equation (2): CP = 1.4623*(T,)-10.1 (reference number 7).

adding cold flow improvers andlor organic solvents to increase
winterization yields also causes an increase in total saturates
which raise directly affect CP of liquid products.
Finally, some products were noted to contain measurable
quantities of residual solvent following in vacuo rotary
evaporation. Experiments showed that small concentrations
(5 wt%) of hexane or isopropanol did not increase CP of
unwinterized SME by more than 2'C.
THERMAL ANALYSES. DSC heating and coolimg
curves for winterized neat SME and SME-additive mixtures are
shown in Figures 3 and 4. Curves were shifted along the Y-axis
(Heat Flow) with respect to constant temperature. Although not
shown, DSC analyses were also conducted on solvent-winterized
SME and SMEadditive mixtures.
Heating and cooling curves for unwinterized SME show
very small peaks (heights s 0.5 Wlg) across the entire
temperature range scanned (-100 to 40°C). In contrast,
winterization radically altered the shape and position of peaks in
the lower melting region (T 5 -20°C) to yield one very large
peak. The lower melting peak appeared near -50°C on the
138
heating curve and -65T on the cooling curve. Winterization
also reduced the size of p-form peaks in the high melting region
(T 2 -20T) for both heating and coolimg curves. In general, the
presence of cold flow improvers during winterization increased
the sue p-form peaks in Fig. 4, with respect to winterized neat
SME. These results were consistent with respect to saturated
methyl ester concentrations discussed above. Winterized SME-
Winfeflowmixtures showed analogousresults for hearing curves
in Fig. 3.
In contrast to heating curves, cooling curves in Fig. 4
showed a distinct baseline shift between 0 and -30°C. The
baselime shift occurs during crystallization in the high melt
region for unwinterized SME and prior to onset of p-form peaks
for winterized neat SME and SME-additive mixtures. Similar
results were observed for solvent-winterized SME and SME-
additive mixtures. Sample mass and cooling rate were constant
during the scans; therefore, the baseline s h i i were an indication
of a decrease in heat capacity caused by a phase transition. In
addition, the phase transition generally took place between -5
and -15'%, that is, winterized products underwent a phase
transition characterized by little or no solid formation because
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

6 8 10 12 14 16 18 20 22
Total Saturates, g l l OOg

Figure 2. Effect of total saturated methylester concentration on CP of methyl esters. Points A

and B are points for unwinterized and winterized neat SME. Line through data corresponds to
Equation (1): CP = 1.4403 *(Total Saturates) - 24.8 (RZ= 0.7906, o2= 5.5762). See Tables 1
and 2 for abbreviations.

Unwinterized

0 - 4
J
No Additives

WinteAow

.-
El-2
m
-

-4, I 1 I I I
-120 -1 00 -80 -6 0 -40 -20 0 20 40
Temperature, "C

Figure 3. DSC heating curves for unwinterized SME, winterized neat SME and winterized SME-additive
mixtures. Curves for winterized products were shifted along Y-axis. See Table 3 for abbreviations.
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

i
o
G
+.
!I
i 3-
-J
- LWinterflow
i t
.-
0 -

::
r_
8 2 -.
W

No Additives
1 - r
L n /
>

Unwinterized

0 , I I
-1 20 -1 00 -80 -60 -40 -20 0 20 40 60
Temperature. ' C

Figure 4. DSC coolmg curves for unwinterized SME, winterized neat SME and winterized SME-additive
mixtures. Curves for winterized products were shifted along Y-axis. T, = crystallization onset temperature
See Table 3 for other abbreviations.

the transition is complete before the onset of the p-form peak.
With respect to deviation from baseline, phase transition
temperatures varied significantly between samples within a
given group of replicates, an indication that they may be
influenced by kinetics. On the other hand, the transitions closely
resemble a glass-type transition from an amorphous liquid phase
to a more ordered liquid phase, such as the formation of a
lamellar phase. Owing to its location relative to studying the
nucleation and crystallization processes of fatty methyl esters,
future thermal analysis of these transitions is warranted. At
present, the location of the p-form peaks, which did not vary
significantly within replicated measurements, was of primary
interest in the determination of onset temperatures.
Completion-of-melt onset temperatures inferred from DSC
heating curves (TI) are listed in Table 3. Also listed are CP-
values calculated from the following equation:
laboratory while SME samples employed in the current studies
were more representative of industrial product. Nevertheless,
under conditions of these studies, winterization with and without
cold flow improvers andlor organic solvents tends to increase
stability during melting of @-formcrystals in the higher melting
region.
Heino (13) reported that CP of distillate fuels may be
determined withim k0.7"C from analysis of DSC cooling curves.
Claudy et al. (16) and Redelius (17) reported similar results for
other petroleum derivatives. In this work, analogous onset
temperatures (T2) were inferred for unwinterized SME,
winterized neat SME and SME-additive mixtures and solvent-
winterized SME and SME-additive mixtures. Least-squares
regression of these T2-valuesresulted in good correlation with
respect to CP. Results are shown in Figure 5. The solid line
drawn through the data corresponds to the following equation:

which was derived earlier from thermal analysis of unwinterized
SME and methyl tallowate admixtures (7). DSC analysis of
winterized products studied in this work gave TI results that
over-predicted CP by 3 to 15OC. Although no Smear relationship
could be inferred, results in this work showed that winterization
of neat SME and SME-additive mixtures as well as soivent-
based winterization of SME and SME-additive mixtures
consistently decreases CP and increases T,. In contrast, Lee
et al. (1 1) reported that winterization of neat SME with and
without organic solvent decreases onset temperature as
&itively expected. Methyl esters in those studies were
prepared and purified via thii-layer chromatography in the
140
where R2 = 0.8834 and u2 = 3.1457. Variances of mean T2-
values from replicate measnrements were very low in the range
0.0020 to 0.8337 indicating excellent repeatability. Therefore,
Equation (3) may be used to predict CP of methyl ester mixtures
from T2-values with an estimated error of only l.S°C, a level
within guidelines for reproducibility outlined in ASTM method
D2500 (18).
Finally, given the nature of CP with respect to total
saturated methyl ester concentration (Fig. 2), it is reasonable to
expect that DSC cooling curves may be analogously employed
to determine total saturated methyl ester content in mixtures.
Earlier comparison of @-formpeak-areas with corresponding
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

Onset(T,). OC

Wint. S M E Winl. SME+PPO A Frae. SME A Frac. SMEIPPO Unwint. SME

Figure 5. Determination of CP from DSC cooling curve onset (T,). CP are mean values (n = 3);
variances s 1.3333. T, are mean values; variances = 0.0020-0.8337. Line through data
corresponds to Equation (3): CP = 1.3653* (T,) + 9.1 (R2= 0.8834, a2= 3.1457). W i t . =
winterized; Unwint. = unwinterized; Frac. =winterized from organic solvent; PPD =cold flow
improver. See Tables 1-3 for other abbreviations.

total saturate concentrations reinforced this notion. For
winterized neat SME, addmg cold flow improvers increased the
total saturates in the liquid product (Table 2), resulting in an
increase in peak area as well as a shift to a higher temperature
(Fig. 4). Although least-squares regression of total saturates
concentration with respect to T, yielded a straight line, its
correspondmg R2was only 0.5991 (aZ= 4.5395),indicating a
considerable degree of experimental scatter.
SUMMARY AND CONCLUSIONS
Winterization of SME-cold flow improver mixtures
significantly enhances liquid product yields and reduces the total
number of process steps, with respect to winterization of neat
SME. Although total saturated methyl ester concentrations were
higher, additives were shown to reduce the rate of occlusion of
unsaturated methyl ester molecules from solution at low
temperatures. Hence, winterization of SME-additive mixtures
gave very good yields of liquid product with substantially
improved cold flow properties.
Solvent-based winterization of SME also resulted in very
good yields of liquid product. Solvents also allowed shorter
equilibration brocess) times than winterization of neat SME or
SMSadditive mixtures. Analogous to neat SME, solvent-based
winterization with added cold flow improvers also increased
yields and decreased equilibration times. These improvements
were compromised by decreased crystalline particle sues that
reduced the removal of saturated methyl ester, which directly led
to an increase in CP. To maintain timely winterization from
1
organic solvents, the addition of cold flow improvers demanded
winterization at lower bath temperatures. Yields were typically
very high (in excess of 95 wt%), indicating that multi-stage
solvent-based winterization processes can be designed to reduce
CP incrementally while maintainimg short process times and
good product yields.
Crystallization onset temperatures for high melting (P-
form) peaks from DSC cooling curves can be measured with
excellent repeatibility. For unwinterized and winterized
products studied in this work, CP correlated linearly with respect
to cooling curve onset temperature (T,). This correlation was
shown to be more accurate at predicting CP than current
standard (ASTM) methodologies. Given the nearly linear
relationship between LTFT and CP of methyl esters established
in earlier reports, thermal analyses of the high melting region
may be useful in developing approaches to improve cold flow
properties of methyl ester mixtures. Furthermore, coolmg curves
appear to be more reliable than heating curves for examinii
low-temperature physical chemistry of methyl ester mixtures.
Finally, cold flow improver- andlor organic solvent-
modified winterization techniques show enormous potential for
improving cold flow properties of alternative diesel fuels from
vegetable oils. However, the key to that potential lies in the
reduction of saturated components in the methyl ester mixture.
Complete reduction of these components is not recommended
because doing so might significantly reduce ignition
quality (19). Thus, exploration of alternative approaches that do
not require large sacrifices in other fuel properties is warranted.
 Downloaded from SAE International by University Of Newcastle, Tuesday, August 07, 2018

ACKNOWLEDGMENTS 13. Heino, E.-L. Determination of Cloud Point for Petroleum

Middle Distillates by Differential Scanning Calorimetry.
A. L. Callison, D. W. Ehmke and H. Khoury provided technical Thermochim. Acta 114, pp. 125-130,1987.
assistance. 14. Chandler, J. E., F. G. Horneck, and G. I. Brown. The Effect
of Cold Flow Additives on Low Temperature Operability of
REFERENCES Diesel Fuels. SAE Technical Paper Series, number 922186,
1992.
1. Schwab, A. W., M. 0. Bagby, and B. Freedman. 15. Owen, K., and T. Coley. Diesel Fuel Low-Temperature
Preparation and Properties of Diesel Fuels from Vegetable Characteristics. Automotive Fuels Handbook, pp. 353-403,
Oil. FUEL 66, pp. 1372-1378,1987. 1990. Society of Automotive Engineers, Warrendaie, PA.
2. Krahl, J., J. Bunger, H.-E. Jeberien, K. Prieger, C. Schutt, 16. Claudy, P., J.-M. Lettofk, B. Neff, and B. Damin. Diesel
A. Munack, and M. Bahadir. Analysis of Biodiesel Exhaust Fuels: Determination of Onset Crystallization Temperature,
Emissions and Determination of Environmental and Health Pour Point and Filter Plugging Point by Differential
Effects. Liquid Fuels and Industrial Products from Scanning Calorimetry. Correlation with Standard Test
Renewable Resources, Proceeding of the Third Liquid Fuel Methods. FUEL 65, pp. 861-864, 1986.
Conference, pp. 149-165, 1996. American Society of 17. Redelius, P. The Use of DSC in Predicting Low
Agricultural Engineers, St. Joseph, MI. Temperature Behaviour of Mineral Oil Products.
3. Masjuki, H. J., A. M. Zaki, and S. M. Sapuan. Methyl Ester Thermochim. Acta 85, pp. 327-330, 1985.
of Palm Oil as an Alternative Diesel Fuel. Fuels for 18. ASTM D2500, Standard Test Method for Cloud Point of
Automotive and Industrial Engines, Proceedings of the 2nd Petroleum Oils. ASTM Standards, Vol. 05.02, pp. 268-270,
Institute of Mechanical Engineering Seminar, pp. 129-137, 1991. American Society for Testing and Materials,
1993. Institute of Mechanical Engineers, London, UK. Philadelphia.
4. Scholl, K. W., and S. C. Sorenson. Combustion of Soybean 19. Harrington, K. J. Chemical and Physical Properties of
Oil Methyl Ester in a Direct Injection Diesel Engine. SAE Vegetable Oil Esters and Their Effect on Diesel Fuel
Spec. Publ. Sp-958: New Developments in Alternative Performance. Biomass 9, pp. 1-17, 1986.
Fuels for Gasolines for SI and CI Engines, pp. 21 1-223.
SAE Technical Paper Series, number 930936, 1993.
5. Clark, S. J., and M. D. Schrock. Soybean Oil Esters as a
Renewable Fuel for Diesel Engines. Final Report for
Project 5980 Performed under Contract 59-2201-6-0-059-0
USDA, ARS, Peoria, IL, 1984.
6. Dunn, R. O., and M. 0. Bagby. Low-Temperature
Properties of Triglyceride-Based Diesel Fuels:
Transesterified Methyl Esters and Petroleum Middle
DistillateEster Blends. J. Am. Oil Chem. Soc. 72, pp. 895-
904, 1995.
7. Dunn, R. O., and M. 0. Bagby. Low-Temperature
Filterability Properties of Alternative Diesel Fuels from
Vegetable Oils. Liquid Fuels and Industrial Products from
Renewable Resources, Proceedings of the Third Liquid Fuel
Conference, pp. 95-103, 1996. American Society of
Agricultural Engineers, St. Joseph, MI.
8. Dunn, R. O., M. W. Shockley, and M. 0. Bagby.
hnproving the Low-Temperature Properties of Alternative
Diesel Fuels: Vegetable Oil-Derived Methyl Esters. J. Am.
Oil Chem. Soc. (in press).
9. Duff, H. G. Winterizing. Introduction to Fats and Oils
Technology (P. J. Wan, ed.), pp. 105-1 13, 1991. American
Oil Chemists' Society, Champaign, IL.
10. Bailey, A. E. Melting and Solidification of Fats, pp. 343-
344, 1950. Interscience, New York.
11. Lee, I., L. A. Johnson, and E. G. Hammond. Reducing the
Crystallization Temperature of Biodiesel by Winterizing
Methyl Soyate. I. Am. Oil Chem. Soc. 73, pp. 631-636,
1996.
12. Formo, M. W. Physical Properties of Fats and Fatty
Compounds. Bailey's Industrial Oil and Fat Production,
Vol. 1,4th Ed. (D. Swern, ed.), p. 214, 1979. Wiley and
Sons, New York.