Energy Fuels 2010, 24, 26522656

Published on Web 03/19/2010

: DOI:10.1021/ef901172t

Oxidation Stability of Palm Methyl Ester: Effect of Metal Contaminants

and Antioxidants
Amit Sarin,*, Rajneesh Arora, N.P. Singh, Rakesh Sarin, and R.K. Malhotra

Department of Applied Sciences, Amritsar College of Engineering and Technology, Amritsar-143001, India, Punjab Technical
University, Jalandhar-144011, India, and Indian oil Corporation Ltd., R&D Centre, Sector-13, Faridabad-121007, India
Received October 14, 2009. Revised Manuscript Received March 10, 2010

The European biodiesel standard EN-14214 calls for determining the oxidation stability (OS) at 110 C
with a minimum induction time of 6 h by the Rancimat method (EN-14112). The ASTM standard D-6751
has recently introduced a minimum induction period of 3 h. Palm methyl ester (PME) has been successfully
evaluated as a diesel substitute in summer and with an additive in winter due to its poor cold-flow
properties. Neat PME exhibited an OS of 9.24 h; thus, it was highly stable. Research was conducted to
investigate the effect of the presence of transition metals, likely to be present in the metallurgy of storage
tanks and barrels, on the highly stable PME. It was found that the influence of metal was detrimental and
catalytic even for stable PME. Small concentrations of metal contaminants showed nearly the same
influence on OS as large amounts. Copper showed the strongest detrimental and catalytic effect.
Antioxidants, namely, tert-butylated hydroxytoluene (TBHT), tert-butylated phenol derivative (TBP),
octylated butylated diphenyl amine (OBPA), and tert-butylhydroxquinone (TBHQ) were doped to
improve the OS of metal-contaminated PME. It was found that the antioxidant TBHQ was most effective
among all of the antioxidants used.

method.7-9 Indian specification IS-15607 also requires a

minimum induction time of 6 h.10,11
The oxidation process is reported in the literature. Relative
rates of oxidation are 1 for oleates, 41 for linoleats, and 98 for
linolenates.12,13 The oxidation chain reaction is usually initiated at the allylic to double bonds. Therefore, fatty acids
with methylene-interrupted double bonds, for example, linoleic acid [(9Z,12Z)-octadecadienoic acid], are more susceptible to oxidation because they contain methylene groups that
are allylic to two double bonds. Fatty acids with two methylene groups, for example, linolenic acid [(9Z,12Z,15Z)-octadecatrienoic acid], are even more susceptible to degradation.
There are several publications on the storage, OS of biodiesel, and effect of antioxidants on the stability of biodiesel.
Dunn has studied the oxidative stability of soybean oil fatty
acid methyl esters by oil stability index (OSI).14 Polavka et al.
studied the OS of methyl esters derived from rapeseed oil and
waste frying oil, both distilled and undistilled, by differential
thermal analysis and Rancimat.15 Ferrari et al. compared the
oxidative stability of neutralized, refined, and frying oil waste
soybean oil fatty acid ethyl ester.16 Mittelbach et al. investigated the influence of different synthetic and natural antioxidants on the OS of biodiesel produced from rapeseed oil,
sunflower oil, used frying oil, and beef tallow, both distilled
and undistilled.17 Dunn has also studied the effect of different

1. Introduction
A number of researchers have investigated alternate renewable fuel sources and concluded that vegetable oil-based fuels
can be used as alternative fuels.1-6 Biodiesel is commercially
produced through the transesterification of vegetable oils,
residual frying oils, or animal fats with alcohol and alkaline
catalysts. Soybean oil and rapeseed are common feedstocks
used for biodiesel production in USA and Europe. However,
Southeast Asian countries such as Indonesia have surplus
palm crops.
The quality of biodiesel is designated by several standards
such as EN-14214 and ASTM D-6751, and oxidation stability
(OS) is among the monitored parameters as the EN-14214
calls for determining oxidative stability at 110 C with a
minimum induction period (IP) of 6 h by the Rancimat
method (EN-14112), and the ASTM standard D-6751
has recently introduced a minimum IP of 3 h by the same
*To whom correspondence should be addressed. E-mail: amit.sarin@
yahoo.com.
(1) Ali, Y.; Hanna, M. A. Bioresour. Technol. 1994, 50, 153163.
(2) Chien, Y.-C.; Lu, M.; Chai, M.; Boreo, F. J. Energy Fuels 2009, 23,
202206.
(3) Qian, J.; Yun, Z. Energy Fuels 2009, 23, 507512.
(4) Ma, F.; Hanna, M. A. Bioresour. Technol. 1999, 70, 115.
(5) Yuan, H.; Yang, B. L.; Zhu, G. L. Energy Fuels 2009, 23, 548552.
(6) May, C. Y.; Liang, Y. C.; Foon, C. S.; Ngan, M. A.; Hook, C. C.;
Basiron, Y. Fuel 2005, 84, 17171720.
(7) Dunn, R. O. J. Am. Oil Chem. Soc. 2002, 79, 915920.
(8) Knothe, G. Energy Fuels 2008, 22, 13581364.
(9) Sarin, A.; Arora, R.; Singh, N. P.; Sarin, R.; Sharma, M.;
Malhotra, R. K. J. Am. Oil Chem. Soc. [Online early access]. DOI:
10.1007/s11746-009-1530-0. Published Online: Dec 29, 2009.
(10) Sarin, A.; Arora, R.; Singh, N. P.; Sarin, R.; Malhotra, R. K.;
Kundu, K. Energy 2009, 34, 20162021.
(11) Sarin, A.; Arora, R.; Singh, N. P.; Sarin, R.; Malhotra, R. K.;
Sarin, S. Energy Fuels [Online early access]. DOI: 10.1021/ef901131m.
Published Online: Feb 16, 2010.
r 2010 American Chemical Society

(12) Frankel, E. N. Lipid Oxidation; The Oily Press: Dundee, Scotland,

1998; p 19.
(13) Hui, Y. H., Ed. Baileys Industrial Oil and Fat Products, 5th ed.;
John Wiley & Sons, Inc.: New York, 1996; Vol. 4, pp 411-415.
(14) Dunn, R. O. J. Am. Oil Chem. Soc. 2005, 82, 381387.
(15) Polavka, J.; Paligova, J.; Cvengros, J.; Simon, P. J. Am. Oil
Chem. Soc. 2005, 82, 519524.
(16) Ferrari, R. A.; Oliveira, V. D.; Scabio, A. Sci. Agric. 2005, 62,
291295.
(17) Mittelbach, M.; Schober, S. J. Am. Oil Chem. Soc. 2003, 80,
817823.

2652

pubs.acs.org/EF

Energy Fuels 2010, 24, 26522656

: DOI:10.1021/ef901172t

Sarin et al.

Table 1. Physico-Chemical Properties of Palm Methyl Ester in Accordance with ASTM D-6751, EN-14214, and IS-15607 Standards10,11

property (units)

ASTM D
6751
ASTM D 6751
test method
limits

EN 14214 test
method

EN 14214
limits

IS 15607 test
method

IS 15607
limits

mean
PME

standard
deviation

EN ISO 3679
EN ISO 3104
EN ISO 3987
EN ISO
20846/20884

min. 120
3.5-5.0
Max. 0.02
max. 0.0010

IS 1448 P:21
IS 1448 P:25
IS 1448 P:4
ASTM D 5453

min. 120
2.5-6.0
Max. 0.02
max. 0.005

138
4.50
0.002
0.003

1.51
0.014
0.0
0.0012

EN ISO 2160
EN ISO 5165

max. 1
min. 51

IS 1448 P:15
IS 1448 P:9
D-2709

max. 1
min. 51
max. 0.05

1
55.3
0.01

0.0
0.10
0.0056

flash point (C)

viscosity at 40 C (cSt)
sulfated ash (% mass)
sulfur (% mass)

D-93
D-445
D-874
D-5453/
D-4294

copper corrosion
cetane number
water and sediment
(vol. %)
conradson carbon residue
(CCR) 100% (% mass)
neutralization value
(mg, KOH/g)
free glycerin (% mass)

D-130
D-613
D-2709

min.130
1.9-6.0
max. 0.02
max. 0.0015
(S 15)
max. 0.05
(S 500)
max. 3
min. 47
max. 0.05

D-4530

max. 0.05

EN ISO 10370

max. 0.3

D-4530

max. 0.05

0.032

0.0055

D-664

max. 0.50

EN ISO 14104

max. 0.5

max. 0.50

0.26

0.025

D-6584

max. 0.02

max. 0.02

max. 0.02

0.01

0.0

total glycerin (% mass)

phosphorus (% mass)
distillation temperature
oxidation stability at
110 C (h)
CFPP (C)

D-6584
D-4951
D-1160
EN 14112

max. 0.24
max. 0.001
90% at 360 C
min. 3 h

EN ISO
14105/14106
EN ISO 14105
EN 14107

IS 1448 P:1/
Sec.1
D-6584

max. 0.25
max. 0.001
min 90%
min. 6 h

0.015
<0.001
>90%
9.24

0.0057
0.013

14

0.57

D 6371

EN ISO 14112

max. 0.25
D-6584
max. 0.0010 D-4951
not under spec.
min. 6 h
EN 14112

EN 116

variable

antioxidants on the OS of biodiesel from soybean oil.18

Thermal and oxidative degradation of castor oil biodiesel
was also investigated.19 Researchers also studied the effects of
oxidation during long-term storage on the fuel properties of
palm oil-based biodiesel.20 Recently, surrogate molecules, i.e.,
methyl, ethyl, isopropyl, and butyl esters of -branched fatty
acid, were synthesized and had substantially better OS, low
temperature flow properties, and cetane number.21 From
these literature reports and quality survey reports,22-24 it
can be concluded that it will not be possible to use biodiesel
without antioxidants.
Recently, Sarin et al. studied the influence of the presence
of five metals, iron, nickel, manganese, cobalt, and copper,
commonly found in the metallurgy of storage tanks and
barrels, on the OS of biodiesel synthesized from nonedible
oil seeds from Jatropha curcas and Pongamia pinnata with
the Rancimat test method.9,25 Loh et al. investigated the
oxidative stability and storage behavior of fatty acid methyl
esters derived from used palm oil,26 and Liang et al. studied
the effect of natural and synthetic antioxidants on the
oxidative stability of palm diesel.27 However, no paper is

IS 1448 P:10

Table 2. Fatty Acid Methyl Ester Composition of Palm

Methyl Ester10,11
fatty acid methyl ester

palm methyl ester (wt %)

palmitic (C16:0)
stearic (C18:0)
oleic (C18:1)
linoleic (C18:2)
saturated
unsaturated

40.3
4.1
43.4
12.2
44.4
55.6

available on the influence of the presence of metals on the

OS of biodiesel from palm. In the present study, we have
undertaken studies on the stability of biodiesel synthesized
from palm. The first objective of this study is to investigate
the influence of the presence of metals on the OS of palm
methyl ester (PME) and then to compare the effects of
various metals on OS with results reported in the literature.25 The second objective is to improve the OS of PME by
doping with various antioxidants and to compare their
effectiveness with results reported in the literature.25 Several
transition metals, iron, nickel, manganese, cobalt, and
copper, commonly found in the metallurgy of storage tanks
and barrels, were blended with varying concentrations in
PME samples.

(18) Dunn, R. O. Fuel Process. Technol. 2005, 86, 10711085.

(19) Conceicao, M. M.; Fernandes, V. J., Jr.; Aranjo, A. S.; Farias,
M. F.; Santos, L. M. G.; Souza, A. G. Energy Fuels 2007, 21, 15221527.
(20) Lin, C.-Y.; Chiu, C.-C. Energy Fuels 2009, 23, 32853289.
(21) Sarin, R.; Kumar, R.; Srivastav, B.; Puri, S. K.; Tuli, D. K.;
Malhotra, R. K.; Kumar, A. Bioresour. Technol. 2009, 100, 30223028.
(22) McCormick, R. L.; Alleman, T. L.; Ratcliff, M.; Moens, L.
Survey of Quality and Stability of Biodiesel and Biodiesel Blends in
the United States in 2004. In National Renewable Energy Laboratory
Technical Report No. NREL/TP-540-38836, 2005.
(23) Alleman, T. L.; McCormick, R. L. Results of the 2007 B100
Quality Survey. In National Renewable Energy Laboratory Technical
Report No. NREL/TP-540-42787, 2008.
(24) Tang, H.; Abunasser, N.; Wang, A.; Clark, B. R.; Wadumesthrige, K.; Zeng, S.; Kim, M.; Salley, S. O.; Hirschlieb, G.; Wilson, J.;
Ng, K. Y. S. Fuel 2008, 87, 29512955.
(25) Sarin, A.; Arora, R.; Singh, N. P.; Sharma, M.; Malhotra, R. K.
Energy 2009, 34, 12711275.
(26) Loh, S.-K.; Chew, S. M.; Choo, Y.-M. J. Am. Oil Chem. Soc.
2006, 83, 947952.
(27) Liang, Y. C.; May, C. Y.; Foon, C. S.; Ngan, M. A.; Hock, C. C.;
Basiron, Y. Fuel 2006, 85, 867870.

2. Experimental Section
2.1. Materials. Methanol used in the synthesis of PME was of
99.8% purity and was purchased from Ranbaxy Fine Chemicals
Ltd. (New Delhi, India). N-Hexane and MeOH/KOH were
of analytical grade and were procured from Merck Specialties
Pvt. Ltd. (New Delhi, India) and Sigma-Aldrich Chemical Co.
(New Delhi, India), respectively. Antioxidants, namely, tertbutylated hydroxytoluene (TBHT), tert-butylated phenol derivative (TBP), octylated butylated diphenyl amine (OBPA), and
tert-butylhydroxquinone (TBHQ), were of analytical grade and
were purchased from Sigma-Aldrich Chemical Co. (New Delhi,
India). Cobalt, manganese, iron, copper, and nickel naphthenates were procured from M/s Notional Chemicals & Dyes Co.
(Varanasi, India).
2.2. Methods. PME was synthesized from refined palm oil in
the laboratory according to the methodology described in the
2653

Energy Fuels 2010, 24, 26522656

: DOI:10.1021/ef901172t

Sarin et al.

Figure 1. Effect of metal contamination (ppm) on the oxidation stability (h) of PME.

literature.28,29 Biodiesel from palm oil was prepared by a

transesterification process, involving the reaction of oil with
methanol under reflux conditions. A series of experiments were
designed to determine the optimal reaction conditions to maximum conversion. Methanol (8:1 molar ratio, alcohol/oil) was
added to the reactor followed by the slow addition of catalyst
(0.6 wt % of oil) with stirring. The stirring was continued until
the complete dissolution of catalyst (15 min). Thus, palm oil
was added, and the reaction temperature was set at 65 C for the
experiment. After the completion of the reaction, the material
was transferred to a separating funnel, and both phases were
separated. The upper phase was methyl ester (biodiesel), and
the lower part was glycerin. Alcohol from both phases was
distilled off under vacuum. The glycerin phase was neutralized
with acid and stored as crude glycerin. The methyl ester was
washed with water twice to remove the traces of glycerin,
unreacted catalyst, and soap formed during transesterification.
The residual product was kept under vacuum to get rid of
residual moisture. The product obtained (>98%) was sufficiently pure for testing. The synthesized PME was tested for
physicochemical properties according to ASTM D-6751, EN14214, and Indian IS-15607 specifications (Table 1).10,11 It is
clear from the data that PME met all of the specifications but
had poor flow properties.
The fatty acid methyl ester composition of PME was determined by gas chromatography on a gas chromatograph (GC)
(PerkinElmer, Clarus 500, New Delhi, India, located at IOC, R
& D Centre, Faridabad), using nitrogen as a carrier gas and a
di(ethylene glycol) succinate column (DEGS) by preparing the
corresponding fatty acid esters and comparing them with standard fatty acid ester samples. The GC was equipped with a flame
ionization detector (FID) and a glass column 3.1 m  2.1 mm
i.d. with a temperature program of 150-250 C (6 C/min, hold
for 20 min). The oven temperature was kept at 200 C; the
injector temperatures were 230 and 250 C. Detailed fatty acid
methyl ester composition (wt %) is given in Table 2.10,11
Metal naphthenates were selected, being highly soluble in
biodiesel. The metal concentration in metal naphthenates was
checked by the ASTM D4951 test method, using inductively
coupled plasma atomic emission spectroscopy. The concentrations of cobalt, manganese, iron, copper, and nickel in their
naphthenates were 5.21, 5.20, 3.91, 6.80, and 4.99%, respectively. The samples were further diluted in PME to the desired
concentration. The concentration of carboxylic acid in metal
naphthenates was practically none (<1%); therefore, their
significance in biodiesel will be insignificant as naphthenates
were blended at the ppm level.

Figure 2. Chemical structures of antioxidants.

The OS of methyl ester in the presence of metal contaminants

and their blends with different dosages of different antioxidants
was measured using Rancimat equipment model 743 (Metrohm,
Switzerland) in accordance with EN-14112.30 In the Rancimat
method, oxidation is induced by passing a stream of air at the
rate of 10 L/h through the biodiesel sample (3 g), kept at constant
temperature 110 C. The vapors released during the oxidation
process, together with air, are passed into the flask containing
50 mL of demineralized water and an electrode for measuring the
conductivity. The electrode is connected to a measuring and
recording device. It indicates the end of the IP when the
conductivity begins to increase rapidly. This accelerated increase
(30) European Committee for Standardization (CEN). Fat and Oil
Derivatives. Fatty Acid Methyl Esters (FAME). Determination of Oxidative Stability (Accelerated Oxidation Test), EN 14112: 2003; European
Committee for Standardization (CEN): Brussels, Belgium, 2003.

(28) Sarin, R.; Sharma, M.; Khan, A. A. Bioresour. Technol. 2009,

100, 41874192.
(29) Vicente, G.; Martinez, M.; Aracil, J. Bioresour. Technol. 2007, 98,
17241733.

2654

Energy Fuels 2010, 24, 26522656

: DOI:10.1021/ef901172t

Sarin et al.

Figure 3. Effect of antioxidant and TBHT concentration (ppm) on the oxidation stability (h) of metal-contaminated (2 ppm) PME.

Figure 4. Effect of antioxidant and TBP concentration (ppm) on the oxidation stability (h) of metal-contaminated (2 ppm) PME.

ppm level) of copper contamination. Even 2 ppm of copper

reduced the IP of PME to below the ASTM D-6751 specification of 3 h. Other metals, namely, iron, nickel, manganese, and cobalt, also had a strong negative influence on the
OS. The presence of copper and cobalt decreased the IP of
PME to even below the ASTM D-6751 limits of 3 h. Figure 1
shows that for all of the metal contaminants, IP values
became almost constant as the concentration of metal increased. This demonstrates that the influence of the metals
was catalytic, but small concentrations of metals have greater negative effect on the OS. These results confirm the effect
of various transition metals, commonly found in the metallurgy of storage tanks and barrels, on biodiesel stability as
reported in the literature.25
3.2.2. Improvement of the OS of Metal-Contaminated
PME. In the present study, antioxidants, namely, TBHT,
TBP, OBPA, and TBHQ, were used (Figure 2). As metallic
impurities have a catalytic effect, a 2-ppm metal concentration was selected for antioxidant dose optimization. All of
the antioxidants were doped into the PME samples with
varying concentrations (at the ppm level), and the corresponding induction periods were measured with the Rancimat test method to observe the effectiveness of different
antioxidants.
Figure 3 shows the variation of IP of PME that was contaminated with 2 ppm of metal with varying concentrations
of the antioxidant TBHT. The OS of metal-contaminated
PME was found to increase with an increase in the dosage of
the antioxidant TBHT. Finally, it was found that a minimum
100 ppm dosage of TBHT was needed to improve the IP of
iron- and nickel-contaminated PME and that a minimum
dosage of 200 ppm of TBHT in manganese-contaminated

is caused by the dissociation of volatile carboxylic acids produced during the oxidation process and absorbed in
the water. When the conductivity of this solution is recorded
continuously, an oxidation curve is obtained whose point of
inflection is known as the IP. Data for all analytical results are
based on triplicate measurements. Subsequent analysis showed
no statistically significant difference between the measurements.
Standard deviations of these measurements are shown in
Table 1.

3. Results and Discussion

3.1. Analyses of PME. The fatty acid methyl ester compositions of the PME samples (Table 2) showed that the PME
mainly consisted of oleic fatty acid methyl esters and palmitic
acid methyl esters. The saturated fatty acid methyl esters in
PME were 44.4%, and the unsaturated fatty acid methyl
esters were 55.6%.
3.2. OS Study. 3.2.1. OS of Neat PME. Neat PME
showed an IP of 9.24 h, which met the minimum limit of 3
h IP in accordance with recent ASTM D-6751 and the
minimum limit of 6 h IP, as required by EN-14112/IS-15607.
3.2.1. Effect of Metal Contaminants on the OS. Different
transition metals, iron, nickel, manganese, cobalt, and copper, commonly found in metal containers, were blended, as
metal naphthenates, with varying concentrations (at the ppm
level) with PME samples. Figure 1 shows that the presence
of these metals depressed the OS of highly stable PME,
as measured by the IP. The presence of metals in biodiesel
resulted in the acceleration of free radical oxidation due to a
metal-mediated initiation reaction.
Copper had the strongest catalytic effect as the IP of PME
decreased drastically even with small concentrations (at the
2655

Energy Fuels 2010, 24, 26522656

: DOI:10.1021/ef901172t

Sarin et al.

Figure 5. Effect of antioxidant and OBPA concentration (ppm) on the oxidation stability (h) of metal-contaminated (2 ppm) PME.

Figure 6. Effect of antioxidant and TBHQ concentration (ppm) on the oxidation stability (h) of metal-contaminated (2 ppm) PME.

PME was needed to meet the EN-14112 specification for

biodiesel OS (Figure 3). Figure 3 also shows that for cobaltand copper-contaminated PME, a minimum dosage of
250 ppm was required to meet EN-14112 specifications.
Figure 4 shows the variation of IP of PME that was
contaminated with 2 ppm of metal with varying concentrations of the antioxidant TBP. It was found that a minimum of
150 ppm dosage of TBP was needed to improve the IP of
iron- and nickel-contaminated PME and that a minimum
dosage of 200 ppm of TBP in manganese-contaminated
PME was needed to meet the EN-14112 specification for
biodiesel OS (Figure 4). Figure 4 also shows that for cobaltand copper-contaminated PME, a minimum dosage of
300 ppm was required to meet the EN-14112 specifications.
The antioxidant OBPA almost showed the same effect as
TBP (Figure 5). These results confirmed that TBHT was the
most effective antioxidant among the first three antioxidants
used, as reported in the literature.25
Further, tests were done with the antioxidant TBHQ.
Figure 6 shows the variation of IP of PME that was
contaminated with 2 ppm of metal with varying concentrations of the antioxidant TBHQ. It was found that a minimum
of 50 ppm dosage of TBHQ was needed to improve the IP of
iron- and nickel-contaminated PME and that a minimum
dosage of 100 ppm in manganese-contaminated PME was
needed to meet the EN-14112 specification for biodiesel OS.
Figure 6 shows that for cobalt- and copper-contaminated
PME, a minimum dosage of 150 ppm was required to meet
the EN-14112 specifications. Therefore, it was found that the

antioxidant TBHQ is the most effective among all of the

antioxidants used. This can be explained on the basis of
the molecular structures of the antioxidants. TBHQ possesses more OH groups attached to the aromatic ring than
the others (Figure 2). Therefore, TBHQ offers more sites for
the formation of complexes between free radicals and antioxidant radicals for lipid stabilization. Hence, TBHQ is more
effective than other antioxidants at the same stage.
Conclusions
The PME used in this work was found to exhibit an OS of
9.24 h in the Rancimat test. The IP of PME decreased
drastically even with small concentrations (ppm level) of metal
contaminants. The influence of the metals on IP was found to
be catalytic, but small concentrations of metals had greater
negative effects on the OS. Of the five metals investigated,
copper appeared to have the strongest detrimental and catalytic effect.
The OS of metal-contaminated PME was found to increase
with increases in the dosage of antioxidants. It was found that
the antioxidant TBHQ was most effective among all of the
antioxidants used. A minimum 50 ppm dosage of TBHQ was
needed to improve the IP of iron- and nickel-contaminated
PME, and a minimum dosage of 100 ppm was needed in
manganese-contaminated PME to meet the EN-14112 specification for biodiesel OS. For cobalt- and copper-contaminated PME, a minimum dosage of 150 ppm was required to
meet EN-14112 specifications.

2656