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: DOI:10.1021/ef9012032
Biodiesel is composed of the monoalkyl esters produced from a variety of animal fats or vegetable oils,
which can be used in blends with conventional petroleum diesel in existing diesel engines. While having
many desirable properties, poor oxidative and storage stabilities are a source of considerable concern.
This paper presents results of studies on the effectiveness of various individual and binary antioxidants
[(R-tocopherol (R-T), butylated hydroxyanisole (BHA), butyl-4-methylphenol (BHT), t-butylhydroquinone (TBHQ), 2,5-ditert-butyl-hydroquinone (DTBHQ), ionol BF200 (IB), propylgallate (PG), and
pyrogallol (PY)] to improve the storage stability of soybean oil (SBO)- and distilled SBO-based biodiesel.
Results indicate that the induction period (IP) of untreated SBO-based biodiesel significantly decreased
with the increasing storage time, while the IP values with adding TBHQ to SBO-based biodiesel remained
constant for up to 30 months. Moreover, the binary antioxidant formulations of THBQ/BHA maintained
the IP of distilled SBO-based biodiesel stable over a 6 month period. TBHQ is the most effective antioxidant to improve the storage stability of SBO-based biodiesel.
1. Introduction
Biodiesel is a domestic, renewable fuel that is gaining wide
acceptance. When blended with conventional petroleum diesel, biodiesel reduces exhaust emissions, improves lubricity,
and can raise the cetane number.1 The promise of biodiesel is
tremendous, but some significant obstacles remain for its
complete acceptance by diesel engine manufacturers. Biodiesel derived from many vegetable oils and animal fats possesses
significant amounts of unsaturated fatty acid methyl ester
(UFAME), and the polyunsaturated fatty acid esters in UFAME
are very prone to oxidative degradation.2 Biodiesel stability is
dependent upon oxidation stability (the influence of oxygen),
thermal stability (the influence of temperature in the absence
of oxygen), and storage stability (the influence of time).3
Biodiesel degradation is caused by an auto-oxidation chain
mechanism.4 The location and number of double bonds in
UFAME affect the susceptibility of the fatty acids chain to
oxygen attack.5 The relative rates of oxidation of methyl
oleate (C18:1), methyl linoleate (C18:2), and methyl linolenate
(C18:3) are 1, 41, and 98, respectively.5 Moreover, environmental factors affect the stability of biodiesel. Leung et al.6
reported that high temperature together with air exposure
greatly increased the biodiesel degradation rate but high
2028
pubs.acs.org/EF
: DOI:10.1021/ef9012032
Tang et al.
Table 1. Detroit Average Temperature (C) from February 2009 to September 2009
maximum (C)
minimum (C)
average (C)
February 2009
March 2009
April 2009
May 2009
June 2009
July 2009
August 2009
September 2009
10
-12
-2
15
-10
3
23
0
9
23
11
16
27
13
19
27
17
21
27
14
22
23
16
19
2. Experimental Section
2.1. Materials. Biodiesel was obtained directly from Biodiesel
Industries (Denton, TX, herein called SBO-I-based biodiesel)
and NextDiesel (Adrian, MI, herein called SBO-II-based
biodiesel). Distilled SBO-II (DSBO-II)-based biodiesel was
produced by vacuum distilling under reduced pressure (3
10-3 torr) and a temperature range of 130-150 C using a
Koehler (Bohemia, NY) K80200 vacuum distillation apparatus.
The antioxidants, R-tocopherol (R-T, 1000 IU/g), BHA (98.5%),
BHT, DTBHQ (99%), PG, TBHQ (97%), PY (99%), heptane
(>99% capillary GC), and N-methyl-N-trimethylsilytrifluoroacetamide (MSTF) were purchased from Sigma-Aldrich, Inc.
(St. Louis, MO). Ionol BF200 (IB) was obtained from Degussa
Sant Celoni (Barcelona, Spain). 1,2,4-Butanetriol [1 mg/mL,
internal standard 1 (ISTD1)] in pyridine was obtained from
Supelco (Bellefonte, PA). Up to 1000 ppm of antioxidants could
dissolve in the biodiesel samples.
2.2. Analysis. 2.2.1. FAME Composition. The FAME composition and content of biodiesel was determined using PerkinElmer Clarus 500 gas chromatography-mass spectrometry
(GC-MS) with a split automatic injector and a Rtx-WAX
(Restek, Bellefonte, PA) column (length, 60 m; inner diameter,
0.25 mm; coating, 0.25 m). Details of the procedure have
been described elsewhere.19 The column was held at 120 C
for 1 min, ramped to 240 C at 20 C/min, and then held at 240 C
for 13 min. The transfer line between GC and MS was kept at
240 C.
2.2.2. Antioxidant Content by GC-Flame Ionization Detector
(FID). The contents of TBHQ and PY were analyzed with a
PerkinElmer Clarus 500 GC-FID. The sample (100 mg) was
mixed with 100 L of ISTD1 and 100 L of MSTFA in a vial and
allowed to sit for 30 min at room temperature. Finally, 2 mL of
heptane was added to the vial. A PE-5HT column (15 m in
length, a 0.32 mm internal diameter, and a 0.1 m film thickness)
obtained from PerkinElmer, Shelton, CT, was held at 50 C for 1 min
and then ramped to 180 C at 15 C/min, 230 C at 7 C/min, and
380 C at 30 C/min. Finally, it was held at 380 C for 10 min.
Hydrogen (99.9999%, Cryogenic Gases, Detroit, MI) was used
as the carrier gas, with a flow rate of 3 mL/min.
2.2.3. Oxidative Stability. Oxidative stability of biodiesel with
and without the addition of the antioxidant was determined according to the Rancimat method using a Metrohm 743 Rancimat
instrument (Herisau, Switzerland). The Rancimat test is the
2029
: DOI:10.1021/ef9012032
Tang et al.
ASTM method
ASTM specificationa
SBO-I
DSBO-II
D 445
D 664
D 6584
D 6584
D 2500
D 97
D 6371
EN 14112
1.9-6.0
0.5 maximum
0.020
0.24
report
4.34
0.22
0.006
0.177
3
-3
-3
3.52
3.99
0.31
0
0
-1
0
-2
0.17
3 minimum
(25) Moser, B. R. Eur. J. Lipid Sci. Technol. 2008, 110 (12), 11671174.
2030
: DOI:10.1021/ef9012032
Tang et al.
Table 3. Effect of Antioxidants on the FAME Content of SBO-I-Based Biodiesel after 18, 24, and 30 Months of Indoor Storage
FAME content by GC-MS
time (months)
control (%)
TBHQ (%)
PG (%)
PY (%)
IB (%)
BHA (%)
R-T (%)
BHT (%)
DTBHQ (%)
0
18
24
30
100
93.1
90.9
87.5
100
97.2
98.2
98.9
100
96.4
96.4
96.4
100
93.7
91.9
88.2
100
96.9
95.2
97.1
100
94.1
92.1
90.0
100
92.3
90.6
86.8
100
96.5
96.0
96.0
100
97.0
94.2
95.1
TBHQ
PY
control
18 months
24 months
30 months
1000
764
677
575
1000
<100
<100
<100
Figure 4. Effect of FAME composition of (a) untreated SBO-Ibased biodiesel, (b) SBO-I-based biodiesel with TBHQ, and (c) SBO-Ibased biodiesel with PY, as a function of the indoor storage time.
: DOI:10.1021/ef9012032
Tang et al.
: DOI:10.1021/ef9012032
Tang et al.
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