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Kapok oil methyl esters

Umer Rashid a, Gerhard Knothe b,*, Robiah Yunus a, Roque L. Evangelista b

a
Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of
Agriculture, 1815 N. University St., Peoria, IL 61604, USA

article info abstract

Article history: The increased need for biodiesel feedstocks has caused various vegetable oils to be examined
Received 9 January 2014 for this purpose. In the present work, the methyl esters of kapok (Ceiba pentandra) oil were
Received in revised form prepared. The essential fuel properties were comprehensively determined and evaluated in
6 February 2014 comparison to specifications in biodiesel standards and some prior results. The kinematic
Accepted 13 February 2014 viscosity of kapok oil methyl esters was greater than expected, an observation traced to the
Available online xxx elevated amounts of methyl esters with cyclic moieties. Overall, kapok oil is a potential
biodiesel feedstock. The 1H and 13C NMR spectra of kapok methyl esters are reported.
Keywords: Published by Elsevier Ltd.
Biodiesel
Fuel properties
Kapok oil methyl esters
Transesterification
Viscosity

sources, other advantages of biodiesel include reduction of

1. Introduction
Renewable fuels from biological resources are receiving ever-
increasing attention as a means to reduce dependence on
fossil fuels. Biodiesel [1,2], which is derived from vegetable
oils, animal fats, waste cooking oils, or potentially other
triacylglycerol-containing feedstocks such as algae, plays a
prominent role among these fuels. A transesterification re-
action of the oil or fat with an alcohol in the presence of a
catalyst, usually hydroxide or, preferably, alkoxide, yields
biodiesel which is defined as the mono-alkyl esters of the
aforementioned sources. Methyl esters are the most common
form of biodiesel due to methanol being the least expensive
alcohol in most countries around the world. Standards for
biodiesel have been established around the world including
ASTM D6751 in the United States [3] and EN 14214 in Europe
[4]. Besides being derived from renewable and domestic
most exhaust emissions with the exception of nitrogen oxides
(NOx), inherent lubricity, high flash point, inherent lubricity,
low or no sulfur content, and a positive energy balance.
Problems associated with the use of biodiesel include poor
cold flow properties, oxidative stability, increase in regulated
NOx exhaust emissions, economics, as well as sufficient
feedstock supply and availability.
The issues of economics, feedstock supply, and availability
have led to an intensive search for additional sources of bio-
diesel beyond the common commodity vegetable oils such as
rapeseed/canola, soybean, palm, and others. Some “alterna-
tive” vegetable oils or other feedstocks that have been studied
include camelina [5], jatropha [6], moringa [7], pongamia [8],
rice bran oil [9], rubber seed [10] and, with currently strong
interest, algae [11e14]. All of these feedstocks yield biodiesel
with fatty acid chains of varying chain length and unsatura-
tion and therefore properties.

* Corresponding author. Tel.: þ1 309 681 6112; fax: þ1 309 681 6524.
E-mail addresses: umer.rashid@yahoo.com (U. Rashid), gerhard.knothe@ars.usda.gov (G. Knothe).
http://dx.doi.org/10.1016/j.biombioe.2014.02.019
0961-9534/Published by Elsevier Ltd.

Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
2 b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 4 ) 1 e7
Kapok (Ceiba pentandra) belongs to the family Malvaceae,
and is a native of tropical America and West Africa. It is now
also found in several Asian regions such as Western India,
Pakistan, Malaysia, Vietnam, Indonesia, and Philippines
[15e17]. The commercial tree species is mostly cultivated in
the rainforests of Asia, especially in Indonesia, Malaysia,
Philippines, China, and South America [15,16]. Malaysian
kapok, locally known as Kekabu, is usually found in northern
parts of Peninsular Malaysia. This tropical tree is famous
among Malay, especially in rural areas [18]. Kapok fruits (pods)
are capsule shaped and contain seeds surrounded by a fluffy,
yellowish fiber made up of a mixture of lignin and cellulose.
No information in terms of definitive numbers, however,
on commercial production of kapok appears to be available.
Similar to other members of the Malvaceae family, commer-
cial interest regarding its utilization has largely focused on its
fiber content, leading to applications of kapok fiber in various
technical textile applications as recently reviewed [19], which
include: thermal and acoustic insulation; buoyancy (stuffing
in life-jackets, lifebelts, mobile pontoons), absorbent proper-
ties, use in composites, nutrition, spinning of kapok (low
cohesivity, therefore in blends with other fibers). Other
recently discussed uses include kapok fiber as source of
cellulosic feedstock for ethanol production [20], for pulp in
papermaking [21], and use in Al-, Cu-, Zn-, Mg-kapok carbon
fiber composites [22]. Kapok fibers, also in the form of de-
rivatives thereof, have been investigated for their high oil
absorption capacities [23e27], which include absorption of
spilled oil [28] and kapok fiber oriented polyaniline for
removing sulfonated dyes from aqueous solution [29].
The oil from kapok, similar to other malvaceous species,
contains malvalic, sterculic, and dihydrosterculic acids [30]
which are characterized by cyclopropane and cyclopropene
rings. Kapok oil, similar to kenaf oil [31], appears to have found
comparatively little interest in the literature compared to the
fiber from these two sources. Several reports exist, however,
on the synthesis of kapok oil methyl esters. In one work, CaO
was used as a catalyst but no fuel properties were reported
[32]. In two other reports, the application of a two-step process
with acid pre-treatment is discussed [33,34] but the fatty acid
profiles disagree with previous literature and some fuel
properties [33,35] appear to be at least partially erroneous.
Another report deals with the optimization of biodiesel pro-
duction from kapok oil [36] but the fatty acid profile also dis-
agrees with other work and no full fuel quality analysis was
described. Thus, to the best of our knowledge, the fuel prop-
erties of methyl esters of kapok oil have not been evaluated
comprehensively in previous literature. The objective of this
work is to evaluate the essential fuel properties of kapok
methyl esters (KpME) and also to evaluate its fatty acid profile
in comparison to previous results.
2. Experimental
Three fruit seed samples (fully ripened kapok pods/fruits) from
three different localities using random sampling design were
harvested at experimental farms in the vicinity of Kuala Kang-
sar, Perak, Malaysia (approximate geographical coordinates
4.5 N, 101 E) under similar environmental conditions. The
Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
seeds were manually separated from the pods, preserved in a
storage bag and then transferred to the laboratory for further
analysis. The ground seeds were extracted in a Soxhlet appa-
ratus with hexane. The mass fraction of oil in the seeds was
determined as 22%. The extracted kapok oil contained a high
mass fraction of free fatty acid (about 16%). Refining was carried
out using different adsorbents and by distillation of FFA. First,
the oil was treated with silica (Trisyl 600, Grace Davison,
Columbia, MD, USA) at 40 g kg1 of oil to remove the phospho-
lipids. The free fatty acid was removed by centrifugal distillation
(Myers Vacuum Lab 3 Still, Kittanning, PA, USA). The rotor
temperature was set at 150  C and vacuum pressure of
1.3e10 kPa (10e60 mTorr). After distillation, the oil was
bleached with 2% activated clay (Tonsil Actisil 220 FF, Süd-
Chemie, Louisville, KY, USA). The oil was further purified using
5% Magnesol (D-Sol D60, Dallas Group of America, Whitehouse,
NJ, USA).
The fatty acid profile of kapok oil was determined on the
methyl esters by gas chromatography (GC) using a Hew-
lettePackard 6890 gas chromatograph equipped with a DBe88
[(88% cyanopropyl) methylarylpolysiloxane] column
(30 m  0.25 mm ID  0.20 mm film thickness) and otherwise as
described in the literature [31]. Retention times were verified
by comparison with authentic fatty acid methyl ester samples.
Additionally, gas chromatography-mass spectrometry (GC-
MS; Agilent Technologies 6890N gas chromatograph coupled
to an Agilent Technologies 5973 mass selective detector) was
performed on the picolinyl (nicotinyl; 3-pyridylcarbinyl) esters
of the oil as described [37] to verify assignments particularly of
the components with cyclic moieties. NMR spectra were ob-
tained with CDCl3 as solvent on a Bruker (Billerica, MA, USA)
Avance 500 spectrometer operating at 500 MHz (1H NMR;
16 scans, time domain size 65,536 points, processed size 32,768
points) or 125 MHz (13C NMR).
The kapok oil obtained above still required reduction of the
acid value which was accomplished following a published
procedure [38] Further transesterification of the kapok oil (60 g
scale) was carried out under standard conditions using 1%
sodium methoxide as catalyst, a 6:1 molar ratio of methanol to
oil at a temperature of 65  C for 1 h. After cooling and phase
separation, the methyl ester phases were washed with water
until neutral by slowly dripping the methyl esters into the
water and permitting them to rise above the water, repeating
this procedure as often as necessary. Finally, the methyl es-
ters were dried with magnesium sulfate. Fuel quality testing
regarding free and total glycerol was carried out with an Agi-
lent Technologies (Santa Clara, CA, USA) 7890A gas chro-
matograph equipped with a cool on-column injector and
Agilent Technologies DB-5HT (high-temperature) column as
described in the standard method ASTM D6584 [39].
Cetane numbers were determined as derived cetane
numbers (DCN) using an Ignition Quality Tester (IQT) as
described previously [40]. The IQT ASTM D6890 is now
approved as an alternative to the traditional cetane number
standard (ASTM D613) in the biodiesel standard ASTM D6751.
Kinematic viscosity was obtained with Cannon-Fenske vis-
cometers employing the standard ASTM D445 as described
previously [41]. Oxidative stability measurements were car-
ried out with a Rancimat (Metrohm, Herisau, Switzerland;
equipped with software for statistical evaluation) using the
 b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 4 ) 1 e7 3

standard EN14112. Lubricity was investigated utilizing a high

Table 1 e Fatty acid profile of the kapok oil used in this
frequency reciprocating rig (HFRR) lubricity tester following
work as determined by gas chromatography (see
the method ASTM D6079 as described in the literature [42]. Experimental section) with comparison to previous work
Cloud and pour point determinations were conducted with a [30,33,34]. Fatty acids are given in order of elution.
phase technology (Richmond, BC, Canada) cloud, pour, and
Fatty acid Present work [30] [33,35] [34]
freeze point analyzer. Density was determined with an Anton
10:0 e e 9.42
Paar (Anton Paar USA, Ashland, VA, USA) DMA 4500M density
14:0 tr 0.1 0.11
meter. Water content was determined by Karl Fischer titration 15.0 e tr
with a Metrohm (Herisau, Switzerland) 831 KF coulometer. 16:0 21.4 21.0e22.4 23.17 23.20
Acid values were determined with the AOCS (American Oil 16:1 0.3 0.3
Chemists’ Society) method Cd3d-63. Analysis of Na, K, P, S, Ca, 17:0 0.1 0.1e0.2
and Mg was performed with a PerkineElmer (Waltham, MA, 17:1 D9 0.5 0.6e0.8
17:2 e 0.6e0.7
USA) Optima 7000 DV ICP-OES spectrometer.
18:0 3.1 2.6e2.7 4.73 5.68
Malvalic 11.5 4.4e8.3
18:1 D9 19.6 21.2e22.6 22.88 29.69
3. Results and discussion 18:1 D11 0.7 1.1e1.3
(18:1 d-11 þ C8cpa)
3.1. Kapok oil Sterculate 1.6e4.8 8.64
C18:2 39.2 36.9e40.4 30 35.11
Dihydrosterculate 2.3 1.5e1.7
The kinematic viscosity of the parent kapok oil was
20:0 0.1 0.5e0.6 1.18 1.89
42.26 mm2 s1, which is higher than that of most vegetable oils 20:1 D9 e 0.1
with kinematic viscosities in the range of the upper 20’s to 22:0 0.4 0.2e0.3 0.25
lower 30’s mm2 s1 at 40  C. The cloud point of kapok oil was 24:0 0.2 e 1.51
0.4  C, and the pour point was 0  C. The oxidative stability per Epoxyoleic 0.1 e
Rancimat test was 0.77 h (standard deviation 0.15). The lu- Others 0.5

bricity by the HFRR test coincided with that of other vegetable

oils with an observed wear scar of 270 mm. The acid value was
acid) and a relatively high amount (8.64%) of sterculic acid but
5.3, equating to 2.4% mass fraction of free fatty acid. The water
no other cyclic fatty acids [33,35], while another publication
content was 457 mg kg1.
does not report any cyclic fatty acid [34], thus both profiles
appear dubious. All reports, however, agree that linoleic acid
3.2. Fatty acid profile and characterization
is the most common fatty acid in kapok oil with oleic and
palmitic acids being the two next most prominent fatty acids.
The KpME synthesized here met the limits in biodiesel stan-
For additional analysis, Fig. 1 depicts the 1H NMR spectrum
dards for the amounts of free and total glycerol, indicating
of KpME and Fig. 2 shows the 13C NMR spectrum of KpME.
high conversion of the oil to the methyl esters.
Terminal CH3 is observed in the 1H NMR spectrum at 0.89 ppm
The fatty acid profile of the kapok oil used here as deter-
and with smaller peaks at 0.98 ppm due to the content of
mined by GC is given in Table 1 with a salient feature of this
methyl linolenate. Furthermore, the 1H NMR spectrum exhibits
profile being the presence of cyclic fatty acids. Prior literature
two complex multiplets at 5.52e5.60 ppm and 5.32e5.44 ppm
data on the fatty acid profile of kapok oil [30,33e35] are also
given in Table 1. Other reports dealing with aspects of the fatty
acid profile of kapok oil are Refs. [43,44].
The aforementioned previous literature on the fatty acid
profile of kapok oil indicated the presence of both malvalic
and sterculic acids as well as their saturated counterparts [30].
A range of 12e14% of cyclopropenoid acids was given by other
authors [44] while approximately 10% (7.1e7.2% malvalic; 2.9%
sterculic acid) was found in another report [43]. A 17:1 fatty
acid noted previously [30] was identified in the present work
as 17:1 D-9 due to the fragmentation pattern of the picolinyl
ester being similar to that of picolinyl oleate. No 17:2 fatty acid
was observed, however, in contrast to the literature [30].
Otherwise, the fatty acid profile is close to that of one previous
report [30]. A minor amount (0.1%) of epoxyoleic acid not re-
ported previously was observed in the present work. Consid-
ering, however, that malvaceous generally exhibit the
“biogenetic oddity” [45] of containing epoxy and cyclic fatty
6.0 5.0 4.0 3.0 2.0 1.0 0
acids simultaneously, the content of epoxy fatty acid is
ppm
apparently lower in kapok oil than in oils from other malva-
ceous species. Another previously reported fatty acid profile in Fig. 1 e 1H NMR spectrum of kapok methyl esters (solvent
work on biodiesel from kapok oil gives 9.4% capric (decanoic CDCl3).

Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
4 b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 4 ) 1 e7
Fig. 2 e 13
C NMR spectrum of kapok methyl esters (solvent
CDCl3).
assignable to the various olefinic protons in the unsaturated
fatty acid chains. Several smaller peaks only visible upon
expansion of the 1H NMR spectrum indicate the presence of
cyclic fatty acids. These peaks include a quartet at 0.31 to
0.34 ppm (assignable to a proton of the methylene carbon in
the cyclopropane ring of methyl dihydrosterculate) and peaks
at 0.55e0.60 (assignable to the second proton of the methylene
carbon in the cyclopropane ring of methyl dihydrosterculate),
0.69 as well as the peak at 0.77 ppm visible in Fig. 1 (assignable
to the CH protons in the cyclopropane ring of methyl
dihydrosterculate).
The peaks in the 13C NMR spectrum of KpME were observed
at 174.31, 174.27, 174.22 (w ¼ weak), 130.20, 130.03, 129.99,
129.73, 128.04, 127.90, 109.53, 109.44 (vw ¼ very weak), 109.21
(vw), 109.13, 51.40, 34.11, 34.09, 31.92, 31.90, 31.87 (vw), 31.52,
(30.21 vw), (30.12 vw), 29.76, 29.68, 29.63, 29.58, 29.51, 29.44,
29.39, 29.35, 29.32, 29.28, 29.25, 29.14, 29.11, 29.09, (29.03 w),
28.97, 2983 (both w), 28.72, 28,67 (both vw), 27.37, 27.29 (vw),
27.19, 27.18, 27.15, 26.02 (vw), 25.97 (vw), 25.92 (vw), 25.62,
24.95, 24.94, 24.89, 22.68, 22.57, 15.77 (vw), 15.73 (vw), 14.09,
14.04, 7.37.
The presence of fatty acid chains with cyclopropene rings
is confirmed by the, albeit weak, peaks in the 109e110 ppm
range, which agrees with literature data [46] given for the
olefinic carbon atoms in such cyclopropene rings. The cyclic
methylene carbon in cyclopropene rings was detected at
about 7.25 ppm [46], agreeing well with the peak observed in
the present work at 7.37 ppm. The peaks at 15.73 and
15.77 ppm agree well with the data for the two chain carbons
in cyclopropane rings [47].
The other peaks in the 13C NMR spectrum correspond to
known assignments, for example, the peaks in the
128e131 ppm range in the 13C NMR spectrum are assigned to
the olefinic carbons in the oleic and linoleic acid chains as well
as the other minor unsaturated fatty acids found in kapok oil;
the peaks at approximately 174 ppm to C1 with the presence
of several peaks are explicable by the presence of the several
fatty acid chains; the peaks at about 14.06 ppm are caused by
Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
terminal CH3; the peaks at about 22.5 ppm correspond to CH2
adjacent to terminal CH3; and the peak at 51.4 ppm to the
carbon originates from CH3 in the methyl ester group. It may
be noted that the present evaluation of the NMR spectra of
KpME resembles that of other methyl esters containing fatty
acid chains with cyclic moieties such as the methyl esters of
kenaf seed [48] and Thespesia populnea [49] oils.
3.3. Fuel properties
Table 2 contains the fuel and physical properties of KpME as
determined during the course of this work. The results are
discussed in more detail below.
3.3.1. Cetane number
The cetane number (as DCN) of KpME was determined as 56.8
[Table 2]. The CNs of methyl linoleate, methyl oleate, and
methyl palmitate, the three major components of KpME, were
determined as 38.2, 59.3, and 85, respectively, in the IQT [39].
The three major components, C16:0, C18:1, and C18:2, together
with C18:0 and minor saturated components, would account
for a CN of approximately 49 calculated according to the
equation [50]
X
CNmix ¼ AC  CNC
in which CNmix is the CN of the mixture that is methyl esters,
AC is the amounts of the individual components, and CNC is
the CN of the individual components.
The compounds for which CNs are known (approximately
85% of the fatty acid profile) would account for a CN of
approximately 49e50. Therefore, the remaining fatty acid
profile, the cyclic compounds which are about 15% of the fatty
acid profile, would account for a CN of about 7e8 and would
indicate a CN of approximately 50. Overall, this is a lower
proportional contribution to the CN than by the cyclic com-
pounds than by the straight-chain compounds. Therefore, it
can be assumed that the neat cyclic fatty compounds have
lower CNs than most straight-chain compounds, at least the
saturated and likely monounsaturated fatty acid chains.
Verifying this experimentally is difficult due to the significant
effort and/or expense in obtaining pure cyclic compounds in
the requisite amounts for cetane testing.
The lower CN of the fatty acids with cyclic moieties is
indicated, however, by other observations. Branched alkanes
have lower CN than straight-chain alkanes with the CN
decreasing if branching occurs towards the center of the chain
[51] and cyclohexane has a lower CN than hexane [50]. The CN
of other biodiesel fuels such as those derived from rapeseed
(canola) or soybean oil generally meets the minimum re-
quirements in biodiesel standards. Also, for the sake of com-
parison, in some previous literature the CN of KpME was given
as 47 [34] and 57.52 [35] while other work gives the cetane
index, a predictive number not necessarily applicable to bio-
diesel, as 57 [36].
3.3.2. Kinematic viscosity
The kinematic viscosity of KpME was determined as slightly
>6 mm2 s1 at 40  C. This value is greater than what could be
expected when considering the kinematic viscosity of the major
straight-chain compounds and also exceeds the maximum
 b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 4 ) 1 e7 5

Table 2 e Fuel properties of kapok methyl esters with comparison to biodiesel standards Refs. [3,4].
Property Kapok methyl esters ASTM D6751 EN 14214
Cetane number 56.8 47 min 51 min
Kinematic viscosity (40  C; mm2 s1) 6.01 1.9e6.0 3.5e5.0
Oxidative stability (h) 0.45 3 min 8 min
Cloud point (EC)a 4.4, 8.1, 4.6 Report e
Pour point (EC) 4.0 e e
Acid value (mg KOH kg1) 57 500 max 500 max
Lubricity (HFRR; mm) 233 520 max (per ASTM D975) 460 max (per EN 590)
Density 15EC (kg m3) 886.38 e 860e900
Density 20EC (kg m3) 882.75 e e
Density 40EC (kg m3) 868.17 e e
Free glycerol mass fraction (%) 0.018 0.02 max 0.02 max
Total glycerol mass fraction (%) 0.071 0.24 max 0.25 max
Monoacylglycerols mass fraction (%) 0.046 e 0.8 max
Diacylglycerols mass fraction (%) 0.148 e 0.2 max
Triacylglycerols mass fraction (%) 0.186 e 0.2 max
Water content (mg kg1) 451 500 max 500 max
Sodium (mg kg1) 40.6 5 max combined 5 max combined
Potassium (mg kg1) 0.6
Phosphorus (mg kg1) 0 10 max 4 max
Sulfur (mg kg1) 13.9 15 max 10 max
Calcium (mg kg1) 1.2 5 max combined 5 max combined
Magnesium (mg kg1) 6.1

For blending with 15 ppm ULSD. 0.05 mass% for blending with 500 ppm sulfur diesel fuel.
a
Report of cloud point in ASTM D6751, cold-filter plugging point with varying limits in EN 14214.

specification in standards. The kinematic viscosity values of the
three major components methyl palmitate, methyl oleate, and
methyl linoleate are 4.38 mm2 s1, 4.51 mm2 s1, and
3.65 mm2 s1 at 40  C [41]. These three esters account for
approximately 80% of the fatty acid profile and would account
for a kinematic viscosity contribution of about 3.28 mm2 s1.
Thus, an overall kinematic viscosity of approximately
4 mm2 s1 could be expected for KpME. According to this
calculation, the remaining approximately 20% of the fatty acid
profile would contribute more to the overall viscosity than
indicated by this amount. Therefore, it is straightforward to
assume that cyclic fatty acids, which account for most of this
20%, possess higher viscosity than their straight-chain coun-
terparts or impart, through molecular interaction, higher vis-
cosity to the mixture. Also, the parent oil displayed a higher
viscosity (42.26 mm2 s1) than could be expected, thus coin-
ciding with the observation on the higher kinematic viscosity of
the methyl esters. On the other hand, kinematic viscosity
values of KpME reported in the literature are 1.8 mm2 s1 [35],
4.17 mm2 s1 [34], and 4.3 mm2 s1 [36]. While the first of these
three values is clearly far too low, the others are in the range
that would be expected when excluding any effect of cyclic fatty
esters but it may be kept in mind that the fatty acid profiles
reported in the two corresponding papers deviate from the
profile reported here and in other literature [30].
A further indication that fatty acid chains with cyclic
moieties may impart higher viscosity to mixtures such as
biodiesel is that cyclohexane possesses significantly higher
kinematic viscosity that hexane [0.93 vs. 0.42 mm2 s1 at 40  C;
[41]]. Furthermore, the kinematic viscosity of kenaf oil methyl
esters, which also contain fatty esters with cyclic moieties,
with methyl epoxy oleate as the major cyclic compound, was
higher than could be expected (4.80 mm2 s1 experimental vs.
approximately 4.10 mm2 s1 expected) [48]. The lesser in-
crease in kenaf methyl esters may be attributed to the
observation that the amount of cyclic acids in kenaf methyl
esters is lower than in kapok methyl esters. An increase in
viscosity was not observed to any significant extent in bio-
diesel from Thespesia oil [52] but the overall amount of cyclic
fatty acids is even lower in this oil.
It may also be noted that biodiesel fuels derived from
commodity and other oils such as rapeseed (canola) or soy-
bean exhibit viscosity range values within expectations by
their fatty acid profiles but they do not contain any or only
trace amounts of cyclic fatty esters.
3.3.3. Cold flow
The cloud point of KpME was observed at a temperature
slightly above 4  C, a temperature that can be expected given
the fatty ester profile with approximately 21% methyl palmi-
tate possessing a melting point of 28.5  C and agreeing with
the observation that the nature and amounts of the saturated
fatty acid methyl esters largely determine the cold flow
properties [53]. There appears to be no detectable effect of the
cyclic moieties in KpME on cloud point, even with a melting
point of methyl dihydrosterculate of 4.4  C [52], an obser-
vation that coincides with the lack of effect of related com-
pounds as potential cold flow-improving additives [54]. The
only other literature value for cold flow properties of KpME is a
cloud point of 1  C [34]. The pour point of KpME was deter-
mined as 4  C, only slightly below the cloud point.
3.3.4. Oxidative stability
The oxidative stability of KpME was determined to be 0.45 h per
the Rancimat test (Table 2). The oxidation stability of the refined
parent oil was 0.77 h. Generally, it has been noted that the

Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
6 b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 4 ) 1 e7
parent oil has significantly higher oxidative stability than the
corresponding methyl esters due to loss of naturally-occurring
antioxidants during the transesterification reaction. The lower
oxidative stability of the parent oil in the case of kapok oil may
possibly be traced to the elevated free fatty acid level although
no unsaturated fatty acid methyl esters meet the minimum
oxidative stability specifications [55] of 3 h in ASTM D6751 [3]
and 8 h in EN 14214 [4]. This also implies that antioxidant ad-
ditives would be required for KpME to meet the minimum
oxidative stability specifications in biodiesel standards.
3.3.5. Density
The density of KpME was determined as 886.4 kg/m3 at 15  C
which is within the range of 860e900 kg/m3 specified in EN
14214 (Table 2; values for density at 20  C and 40  C also given
there). This aspect, however, may not be that critical because
the density specification in EN 14214 likely serves the purpose
to exclude vegetable oils (triacylglycerols).
3.3.6. Lubricity
KpME exhibits excellent lubricity as documented by a wear
scar value of 233 mm in the HFRR lubricity test (Table 2), well
below the maximum wear scar values of 520 and 460 mm
prescribed in the petrodiesel standards ASTM D975 [56] and
EN 590 [57], respectively. The results agree well with the
known high lubricity of vegetable oil methyl esters [42,58].
3.3.7. Other specifications
KpME met the specifications for acid value. The values for
three heteroelements in biodiesel standards, Na, Mg, and S,
were slightly elevated, however, all three are present either in
the transesterification catalyst or drying agent, indicating
these materials as likely origin. The values for K, P, and Ca
were well below the limits prescribed in biodiesel standards.
4. Conclusions
Overall, kapok oil methyl esters are competitive with methyl
esters of other oils in terms of fuel properties with the exception
of somewhat elevated kinematic viscosity. The results
regarding kinematic viscosity indicate, in conjunction with prior
literature, that cyclic fatty esters possess elevated kinematic
viscosity, imparting this feature to the mixture that is biodiesel.
Disclaimer
Mention of trade names or commercial products in this pub-
lication is solely for the purpose of providing specific infor-
mation and does not imply recommendation or endorsement
by the U.S. Department of Agriculture. USDA is an equal op-
portunity provider and employer.
Acknowledgment
We thank Kevin R. Steidley for excellent technical assistance,
Kim Ascherl for ICP analysis, Dr. Karl Vermillion for obtaining
Please cite this article in press as: Rashid U, et al., Kapok oil methyl esters, Biomass and Bioenergy (2014), http://dx.doi.org/
10.1016/j.biombioe.2014.02.019
the NMR spectra, all of USDA/ARS/NCAUR, and Barrett Man-
gold (Southwest Research Institute, San Antonio, TX) for ce-
tane number determination.
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