Article

pubs.acs.org/EF

Antioxidant Consumption Kinetics and Shelf-Life Prediction for

Biodiesel Stabilized with Antioxidants Using the Rancimat Method
Jian Zhou,* Yun Xiong, and Yonggang Shi
Department of Fuel Chemistry, Logistical Engineering University, Chongqing 401331, People’s Republic of China

ABSTRACT: Kinetic studies on the oxidation of biodiesel and the consumption of antioxidants were performed in this work,
using the standard Rancimat method within the temperature range of 100−150 °C. On the basis of the length of induction
period, antioxidant efficiency was ranked in the descending order of tert-butylhydroquinone (TBHQ) > pyrogallol (PY) > propyl
gallate (PG) > butylated hydroxyanisole (BHA) > butylated hydroxytoluene (BHT). The natural logarithm of the initial
antioxidant concentration varied linearly with respect to the induction period. Kinetic information for the consumption of the
antioxidant could be obtained by pseudo-first-order reaction assumptions. TBHQ had the lowest consumption rate, followed by
PG, PY, BHA, and BHT; the lower consumption rate seemed to lead to a longer induction period. The critical antioxidant
concentration increased in the ascending order of PY < PG < BHA < BHT < TBHQ, basically in accordance with the order of
antioxidant efficiency, except TBHQ. The apparent activation energy for the consumption of the antioxidant was determined
using the Arrhenius equation: TBHQ (97.85 kJ/mol), PG (96.91 kJ/mol) > BHT (91.74 kJ/mol) > PY (82.76 kJ/mol) > BHA
(80.08 kJ/mol), which agreed well with the order of activation energy for the oxidation of biodiesel. TBHQ, PG, and BHT, more
temperature sensitive than PY and BHA, showed higher susceptibility to oxidative degradation at a higher temperature. The shelf
life of biodiesel at ambient temperature was predicted with the extrapolation method and ranked in the descending order of
TBHQ > PG > PY > BHT > BHA, basically in line with the order of the reaction constant of antioxidant consumption.

1. INTRODUCTION pyrogallol (PY), propyl gallate (PG), butylated hydroxyanisole

As a result of the growing concern on environmental protection (BHA), and butylated hydroxytoluene (BHT).7 These phenolic
and energy security, biodiesel has received increasing world- compounds could break the chain propagation by donating
wide attention as a renewable alternative biofuel. Biodiesel hydrogen atoms to active free radicals, and the stable
consists of long-chain fatty acid esters derived from vegetable antioxidant radicals do not initiate another radical reaction or
oils, animal fats, and waste cooking oils and offers many propagate the oxidation process.1,2,4,6,7
advantages over conventional petroleum diesel, such as It is known that antioxidants can be gradually consumed by
inherent biodegradability, enhanced lubricity, improved safety, scavenging free radicals during the antioxidative process. When
and reduced exhaust emissions.1,2 The study of biodiesel in antioxidants are consumed to critical levels, the induction
recent years is primarily focused on the following aspects: period will be over and the oxidation will proceed at the same
feedstock selection, production technology, engine perform- rate as that in the absence of antioxidants.8,9 The testing
ance, oxidation stability, and cold flow behavior. The resistance temperature has significant influence on the kinetic behavior of
of biodiesel against oxidation has always been a priority concern antioxidant consumption and biodiesel oxidation. A higher
to suppliers, distributors, and users. As a result of the presence testing temperature leads to a faster reaction rate and shorter
of unsaturated methyl esters of oleic, linoleic, and linolenic analysis time.10 Richaud et al.11 investigated the oxidation
acids, biodiesel has high susceptibility to oxidative degradation, kinetics of methyl oleate, methyl linoleate, and methyl
which could result in the deterioration of fuel quality and linolenate at 90, 110, 140, and 150 °C using the
engine performance as well as exhaust emissions.3,4 The chemiluminescence method. Induction time and maximal
oxidation stability of biodiesel is usually characterized by the steady-state intensity seemed to obey the Arrhenius law in
length of induction period by the Rancimat method. According the temperature range studied, and a lower temperature
to the newest EN 14214:2014 standard, a minimum induction resulted in a longer induction period and lower maximal
period of 8 h is required to ensure biodiesel quality.5
intensity.
The use of antioxidants is the most widely accepted practice
Kinetic parameters, such as reaction order, reaction rate, and
for improving the oxidation stability of biodiesel. The efficiency
apparent activation energy, could be obtained by subjecting fuel
of antioxidants to inhibit the oxidation of biodiesel depends
upon many factors, including their chemical structures, samples to heat treatment at different temperatures. Pereira et
interactions with the substrate, and type of stability test al.10 examined the effect of the temperature on the oxidation
methods used to evaluate antioxidant performances.6 From the behavior of soybean biodiesel at room temperature, 60, and 110
economical point of view, antioxidant concentrations should be °C, by monitoring the increase of peroxide values as well as
within the range of 200−1000 ppm. The following synthetic
antioxidants are generally more preferred than natural Received: August 31, 2016
antioxidants because of their higher effectiveness when they Revised: November 7, 2016
are added to biodiesel: tert-butylhydroquinone (TBHQ), Published: November 8, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.6b02199

Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Article

parallel loss of natural tocopherols. The results indicated that the consumption of antioxidants, and to predict the shelf life of
the evolution of hydroperoxides during the induction period the biodiesel at ambient temperature.
followed zero-order reaction kinetics. A similar kinetic study for
hydroperoxide formation in sunflower/rapeseed biodiesel at 80, 2. EXPERIMENTAL SECTION
85, 90, and 95 °C was carried out by Dinkov et al.12 using the The biodiesel used in this study was obtained through the
modified ASTM D2274 method. The average reaction order for transesterification of waste cooking oil and provided by Chengdu
hydroperoxide formation was about 0.47, and the shelf life of Hengrun Hi-Tech Co., Ltd., Sichuan, China. The fresh biodiesel was
known to contain no antioxidant additives, and its main
the studied biodiesel via extrapolation was between 1.17 and
physiochemical properties as well as fatty acid compositions were
1.27 years. Borsato et al.13 evaluated the oxidation kinetics of given in Table 1. The Agilent 7890A gas chromatography (GC)
soybean biodiesel stabilized with BHA, BHT, and TBHQ by
submitting fuel samples to an accelerated oven test at 30, 50, Table 1. Main Physiochemical Properties of the Waste
and 80 °C, in which the biodiesel oxidation presented a first- Cooking Oil Biodiesel and Its Fatty Acid Profile
order reaction in the presence and absence of antioxidants.
The Rancimat method specified in the EN 14214 standard fatty acid methyl content
property value ester (%, w/w)
uses a temperature of 110 °C to determine the oxidation
stability of biodiesel. If possible, the temperature can be further viscosity at 40 °C (mm2/s) 4.20 myristic acid 0.59
(C14:0)
raised to 130 °C to shorten the analysis time.14 However, many
density at 15 °C (g/cm3) 0.878 palmitic acid 15.53
previous studies have been conducted at temperatures lower (C16:0)
than 120 °C, partly as a result of concerns that some CFPP (°C) 5 palmitoleic acid 1.27
antioxidants may volatilize and decompose at a high temper- (C16:1)
ature.8,9,15 Because temperatures have different effects on the flash point (°C) 159 stearic acid 6.80
(C18:0)
antioxidant activity in inhibiting the oxidation of biodiesel,
cetane number 54.0 oleic acid (C18:1) 41.53
antioxidants may have different reaction mechanisms under
sulfur content (ppm) <1 linoleic acid 27.78
different experimental conditions.16,17 As far as we know, there (C18:2)
is little knowledge about the kinetic behavior of antioxidants at water content (ppm) 300 linolenic acid 1.10
temperatures higher than 130 °C using the Rancimat method (C18:3)
and only limited information is currently available regarding acid number (mg of KOH/g) 0.37 arachidic acid 0.41
(C20:0)
how the antioxidant performances are influenced by abusive
copper strip corrosion 1.0 eicosenoic acid 1.44
temperatures. It is important to establish whether oxidation (∼3 h at 100 °C) (C20:1)
stability determined at one temperature could be correlated oxidation stability at 110 °C 3.01 behenic acid 0.24
with that obtained at another temperature.18 (h) (C22:0)
Dunn19 investigated the effect of the block temperature (T) ester content (%, w/w) 98.96 erucic acid 2.27
(C22:1)
on the oil stability index (OSI) of soybean (60−80 °C) and
used cooking oil (75−95 °C) biodiesels. Two mathematical
models demonstrated good linear correlations for both
biodiesels studied, ln(OSI) versus T (°C), and ln(OSI) versus system equipped with a 5975C mass selective detector (MSD) and a
T−1 (K), and the second model could be employed to calculate HP-5MS column (30 m × 250 μm × 0.25 μm) was used for
the apparent activation energy of the first-order reaction of chromatographic analysis. The column heating ramp began at 180 °C
biodiesel oxidation. Xin et al.8 studied the oxidation kinetics of (held for 3 min), then ramped at a rate of 1 °C/min to 200 °C (held
safflower biodiesel stabilized with propyl gallate at temperatures for 2 min), and last heated at a rate of 20 °C/min to 250 °C (held for
from 100 to 120 °C using the Rancimat method. The reaction 2 min). The injection volume was 1 μL, and a split ratio of 100:1 was
rate of propyl gallate consumption fitted well with the employed. More detailed description of this procedure has been
Arrhenius law, and the activation energy for propyl gallate described elsewhere.20 The five most commonly used synthetic
antioxidants, i.e., TBHQ, PY, PG, BHA, and BHT, purchased from
consumption was calculated as 97.02 kJ/mol. Aladdin Industrial Corporation (analytical grade), were added to the
Although there are reports dealing with the effect of the biodiesel at concentrations of 100, 250, 500, 750, and 1000 ppm (by
temperature on the oxidation stability of biodiesel, few weight). The chemical structures of these antioxidants were shown in
conclusive results associated with the detailed kinetics of Scheme 1.
biodiesel oxidation and antioxidant consumption have been The oxidation stability was determined by the induction period
reached. Most previous studies involving biodiesel oxidation using an 873 Biodiesel Rancimat instrument from Metrohm according
stability were focused on ranking the antioxidant efficiency to the EN 14112 standard. The Rancimat method allows for
simultaneous analysis of up to eight samples using two independently
based on the length of the induction period. To the best of our thermostat-controlled heating blocks. When purified air is blown
knowledge, few attempts were made to reveal more kinetic through the samples (3 ± 0.2 g) at the rate of 10 L/h, the experiments
information, such as the reaction rate and activation energy, were carried out at constant temperatures of 100, 110, 120, 130, 140,
about the temperature dependence of antioxidant consumption and 150 °C and reference temperature correction values of 0.8, 0.9,
and biodiesel oxidation during the antioxidative process. On the 1.0, 1.1, 1.1, and 1.2 °C were provided in the Rancimat user manual,
basis of this background, the effects of the temperature on the respectively. Afterward, the volatile oxidation products were swept out
oxidation of biodiesel stabilized with most often used and collected in the measuring vessel containing 50 mL of deionized
water, where the electrical conductivity was monitored continuously.
antioxidants, BHA, BHT, PY, PG, and TBHQ, were
The induction period was defined as the time required to cause a
investigated in this study, at temperatures ranging from 100 sudden increase in conductivity. All measurements were carried out in
to 150 °C using the standard Rancimat method. The purpose quadruplicate and expressed as the mean ± standard deviation (SD).
of this work was to determine the kinetic data for the oxidation The coefficient of variation (CV) of less than 5% indicated good
of biodiesel, to investigate the antioxidative characteristics for repeatability of this method.

B DOI: 10.1021/acs.energyfuels.6b02199
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Article

Scheme 1. Chemical Structures of the Five Synthetic moreover, that the difference between the antioxidant
Antioxidants Used in This Study efficiencies of PY and PG decreased with the increasing
concentration, especially at higher concentration levels. Overall,
the antioxidant efficiency was in the descending order of
TBHQ > PY > PG > BHA > BHT, in agreement with earlier
observations by Mittelbach et al.2 Obviously, this order of
antioxidant efficiency was consistent in the temperature range
of 110−140 °C.
The differences in the antioxidant efficiency could be largely
attributed to their chemical structures.2,3,7,9,23 TBHQ, PY, and
PG have at least two active hydroxyl groups on their benzene
rings, making them more easily donate hydrogen atoms to free
radicals than BHA and BHT to interrupt the chain propagation.
The antioxidant potencies of the monohydric BHA and BHT
may not be fully realized during the experiments as a result of
possible decomposition and volatilization losses.24 During the
antioxidative process of TBHQ, the derivative compounds
formed may also retain antioxidant properties, and some of
them were even reported to have higher activity than TBHQ
3. RESULTS AND DISCUSSION itself.25,26
3.1. Biodiesel Characterization. The biodiesel used in 3.3. Antioxidant Consumption Kinetics. The depend-
this work was derived from waste cooking oil, which is one of ence of the oxidation stability of biodiesel upon the antioxidant
the major feedstocks for biodiesel production in China.17 concentration is clearly illustrated in Figure 1. These
Biodiesel made from waste cooking oil usually has high antioxidants showed a sharp increase in the induction period
contents of unsaturated fatty esters and, therefore, shows at concentrations lower than 250 ppm, followed by a slight
noticeably poor oxidation stability in many previous studies.21 increase at concentrations higher than 500 ppm. The increase
As seen from Table 1, this biodiesel fulfilled the EN in the induction period with an increasing antioxidant
14214:2014 quality specifications with the exception of the concentration appears to be nonlinear and possibly exponential,
oxidation stability, which could be ascribed to its high which was also observed in previous studies.8,9 Considering that
unsaturated fatty ester contents. This biodiesel had 23.57% of the consumption of the antioxidant depends upon its initial
saturated fatty esters, 46.51% of monounsaturated fatty esters, concentration, the pseudo-first-order reaction kinetics may be
and 28.88% of polyunsaturated fatty esters. The predominant used to describe the antioxidant consumption mechanism: dC/
fatty ester was methyl oleate (C18:1, 41.53%), followed by dt = −kC.27 When the antioxidants were gradually consumed
methyl linoleate (C18:2, 27.78%) and methyl palmitate (C16:0, by free radicals from initial concentration C0 to critical
15.53%). The composition profile of this biodiesel agreed well concentration Ccr at the end of the induction period, they
with previous reports that also chose used frying oil as raw were assumed to be no longer effective to retard the oxidation
material.2,14,22 of the biodiesel. After integration within the concentration
3.2. Rancimat Induction Period. The Rancimat induction (from C0 to Ccr) and time (from IP0 to IP) limits, the above
period values obtained at 100−150 °C for biodiesel treated equation can be written as ln C0 = k(IP − IP0) + ln Ccr, where
with antioxidants are presented in Table 2. A good repeatability C0 and Ccr are the initial and critical concentrations (×106,
of this method could be confirmed with a coefficient of ppm) of the antioxidant in the biodiesel, IP and IP0 are the
variation of lower than 5% in all cases. The untreated biodiesel induction periods (h) of the biodiesel treated and untreated
showed only 3.01 h induction period at 110 °C, which failed to with antioxidant, and k is the reaction constant (h−1) of the
meet the minimum 8 h oxidation stability requirement antioxidant consumption.
prescribed in the EN 14214:2014 specification. As seen in As seen from Figure 2, there is a good fit for all antioxidants
Table 2, the addition of antioxidants could noticeably extend between the logarithm of the initial concentration ln C0 (×106,
the induction period. The longer the induction period, the ppm) and the induction period IP (h) at each temperature,
better the oxidation stability. Both the testing temperature and with the coefficient of determination R2 exceeding 0.9116. The
antioxidant concentration had significant influences on the reaction constant k (h−1) for the consumption of antioxidants
length of the induction period. The lower the temperature, the can be determined from the slope of these fitted lines. After
longer the induction period. In addition, the higher the substitution of the reaction constant k (h−1) and the initial
concentration, the better the oxidation stability. concentration C0 (ppm) into the equation ln C0 = k(IP − IP0)
PY gave the highest induction period value at 100 ppm, + ln Ccr, the critical concentration Ccr (ppm) can be obtained as
followed by TBHQ, PG, BHA, and BHT. At concentrations well, as shown in Table 3.
greater than 250 ppm, the effectiveness of antioxidants was not We can see clearly from Table 3 that both reaction constant k
in the same order: TBHQ showed the best oxidative stability, and critical concentration Ccr increased with an increasing
followed by PY, PG, BHA, and BHT. From the table, we can temperature. The reaction constant almost doubled for a 10 °C
see that BHA was slightly better than BHT at all concentration rise in the temperature. A higher k indicated a faster rate of
levels, while TBHQ, PY, and PG were far more efficient than consumption and, possibly, a lower antioxidant efficiency. The
the former according to their induction period values. A total of consumption of BHT was slightly slower than BHA at lower
100 ppm of TBHQ and PY could match 1000 ppm of BHA and temperatures (<110 °C) but much faster than the latter at
BHT; almost 500 ppm of BHA and BHT were needed to higher temperatures (>120 °C). The difference between the
satisfy the requirement of the specification. It should be noted, consumption rates of BHT and BHA increased markedly with
C DOI: 10.1021/acs.energyfuels.6b02199
Energy Fuels XXXX, XXX, XXX−XXX
 Table 2. Oxidation Stability of Biodiesel Stabilized with Antioxidants Determined at 100−150 °C
Rancimat induction period (h)
100 °C 110 °C 120 °C 130 °C 140 °C 150 °C
mean ± SD CV (%) mean ± SD CV (%) mean ± SD CV (%) mean ± SD CV (%) mean ± SD CV (%) mean ± SD CV (%)
Energy & Fuels

blank 6.62 ± 0.25 3.83 3.01 ± 0.03 0.94 1.54 ± 0.01 0.92 0.61 ± 0.01 0.95 0.31 ± 0.01 3.11
100 ppm PY 16.11 ± 0.30 1.87 7.07 ± 0.14 1.94 3.07 ± 0.04 1.21 1.45 ± 0.02 1.65 0.74 ± 0.01 1.10
TBHQ 12.36 ± 0.26 2.07 5.42 ± 0.10 1.82 2.22 ± 0.02 0.93 1.16 ± 0.02 1.30 0.57 ± 0.01 2.20
PG 10.07 ± 0.24 2.37 4.29 ± 0.11 2.59 1.94 ± 0.01 0.42 0.86 ± 0.02 2.03 0.44 ± 0.01 1.86
BHA 11.35 ± 0.08 0.72 4.94 ± 0.07 1.48 2.35 ± 0.02 0.92 1.08 ± 0.01 0.76 0.56 ± 0.02 3.45
BHT 10.67 ± 0.05 0.51 4.55 ± 0.02 0.40 2.25 ± 0.07 3.12 0.95 ± 0.02 2.11 0.46 ± 0.00 1.08
PY > TBHQ > PG > BHA > BHT
250 ppm TBHQ 22.30 ± 0.41 1.83 9.92 ± 0.06 0.56 4.31 ± 0.08 1.77 1.93 ± 0.01 0.50 0.97 ± 0.01 0.84
PY 20.07 ± 0.74 3.71 8.81 ± 0.14 1.64 4.19 ± 0.01 0.31 2.03 ± 0.01 0.64 1.08 ± 0.02 1.39
PG 15.10 ± 0.42 2.79 6.53 ± 0.16 2.38 2.83 ± 0.06 2.10 1.39 ± 0.02 1.25 0.70 ± 0.01 1.86
BHA 15.53 ± 0.09 0.56 7.24 ± 0.10 1.32 3.41 ± 0.02 0.63 1.60 ± 0.03 1.61 0.82 ± 0.01 1.54
BHT 14.32 ± 0.29 2.06 6.27 ± 0.08 1.29 2.87 ± 0.05 1.72 1.30 ± 0.02 1.15 0.63 ± 0.01 2.24
500 ppm TBHQ 33.45 ± 0.41 1.23 15.00 ± 0.05 0.35 6.90 ± 0.06 0.85 3.33 ± 0.03 0.79 1.69 ± 0.08 4.87
PY 22.70 ± 0.38 1.67 10.48 ± 0.20 1.93 5.06 ± 0.22 4.36 2.50 ± 0.04 1.55 1.32 ± 0.02 1.68
PG 19.57 ± 0.21 1.10 8.64 ± 0.20 2.33 3.85 ± 0.10 2.54 1.87 ± 0.01 0.51 0.98 ± 0.02 1.78
BHA 19.22 ± 0.27 1.41 9.18 ± 0.14 1.56 4.33 ± 0.04 1.04 2.16 ± 0.02 0.79 1.13 ± 0.01 1.15
BHT 18.16 ± 0.22 1.21 8.29 ± 0.03 0.42 3.75 ± 0.09 2.42 1.74 ± 0.04 2.5 0.86 ± 0.01 0.95

D
750 ppm TBHQ 36.82 ± 0.50 1.36 17.10 ± 0.33 1.91 7.86 ± 0.34 4.29 3.89 ± 0.08 2.14 1.81 ± 0.04 2.08
PY 24.34 ± 0.53 2.17 11.45 ± 0.15 1.33 5.46 ± 0.05 0.96 2.74 ± 0.03 0.91 1.45 ± 0.02 1.18
PG 22.73 ± 0.24 1.04 10.24 ± 0.23 2.26 4.65 ± 0.04 0.88 2.23 ± 0.02 1.00 1.12 ± 0.01 0.86
BHA 21.12 ± 0.21 1.00 10.23 ± 0.08 0.79 5.02 ± 0.04 0.84 2.44 ± 0.04 1.47 1.35 ± 0.01 0.96
BHT 20.74 ± 0.23 1.11 9.63 ± 0.14 1.45 4.46 ± 0.05 1.15 2.07 ± 0.06 2.68 1.01 ± 0.02 1.70
1000 ppm TBHQ 51.12 ± 0.12 0.23 22.78 ± 0.27 1.18 10.79 ± 0.15 1.43 5.19 ± 0.15 2.81 2.60 ± 0.04 1.38
PY 25.89 ± 0.39 1.50 11.61 ± 0.05 0.40 5.71 ± 0.12 2.14 2.91 ± 0.10 3.58 1.54 ± 0.02 1.53
PG 24.51 ± 0.47 1.93 11.01 ± 0.23 2.08 5.13 ± 0.05 0.99 2.45 ± 0.01 0.51 1.27 ± 0.01 0.76
BHA 22.52 ± 0.33 1.45 11.10 ± 0.21 1.92 5.43 ± 0.07 1.28 2.78 ± 0.00 0 1.47 ± 0.01 0.96
BHT 22.87 ± 0.40 1.75 10.83 ± 0.12 1.14 5.03 ± 0.06 1.19 2.36 ± 0.03 1.40 1.17 ± 0.01 0.70
TBHQ > PY > PG > BHA > BHT
Article

DOI: 10.1021/acs.energyfuels.6b02199
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Article

Figure 1. Influence of the antioxidant concentration on biodiesel oxidation stability determined at 100−150 °C.

Figure 2. Natural logarithm of the initial antioxidant concentration versus Rancimat induction period determined at 100−150 °C.

Table 3. Reaction Constant k (h−1), Critical Concentration Ccr (ppm), and Coefficient of Determination (R2) for Consumption
of Antioxidants at Various Temperatures
TBHQ PY PG BHA BHT
2 2 2 2
k Ccr R k Ccr R k Ccr R k Ccr R k Ccr R2
100 °C 0.2044 38.72 0.9992 0.1872 53.30 0.9868
110 °C 0.0606 79.03 0.9305 0.2401 4.42 0.9984 0.1574 33.66 0.9962 0.3741 50.40 0.9993 0.3622 68.20 0.9798
120 °C 0.1351 81.14 0.9476 0.4779 6.99 0.9918 0.3353 40.61 0.9931 0.7417 56.99 0.9949 0.7984 73.02 0.9579
130 °C 0.2720 90.17 0.9395 0.8563 11.02 0.9970 0.7029 43.76 0.9811 1.3585 61.79 0.9884 1.5982 71.86 0.9685
140 °C 0.5607 91.69 0.9331 1.5635 16.29 0.9995 1.4305 48.11 0.9936 2.4387 59.73 0.9850 3.1981 79.95 0.9643
150 °C 1.1210 0.9116 2.8579 0.9991 2.7720 0.9906

E DOI: 10.1021/acs.energyfuels.6b02199
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Article

the increasing temperature, which could be due to volatilization consumption of the antioxidant can be calculated from the
and decomposition losses of the former at a high temperature slope of the line (−Ea/R) and ranked in the following order:
employed. Considering the better antioxidant efficiency of PY TBHQ (97.85 kJ/mol), PG (96.91 kJ/mol) > BHT (91.74 kJ/
than PG based on the length of the induction period, the latter mol) > PY (82.76 kJ/mol) > BHA (80.08 kJ/mol). The Ea
presented an unexpected slower rate of consumption and the value of propyl gallate was confirmed with the activation energy
difference between the consumption rates of PY and PG of PG consumption (97.02 kJ/mol) in safflower biodiesel
decreased with the increasing temperature. Overall, the reaction reported by Xin et al.8 The activation energy is equal to the
constant increased in the following order: TBHQ < PG < PY < energy barrier that must be overcome for a chemical reaction to
BHA < BHT. occur. The faster rate of consumption of PY was in line with its
On the basis of the assumption of the first-order decay, the lower activation energy than PG. According to Tan et al.28 and
lower critical concentration could be associated with higher Hashemi et al.,29 a higher Ea indicates a smaller temperature
antioxidant efficiency. PY had the lowest critical concentration, change needed to induce a certain change in the rate of
followed by PG, BHA, BHT, and TBHQ, basically in line with oxidation. The reactions with higher Ea are more temperature-
the order of antioxidant efficiency, except TBHQ. TBHQ sensitive, and reactions with lower Ea are less temperature-
showed the best oxidation stability and lowest consumption sensitive.30 Despite the faster rate of consumption, BHT
rate, while it also required the highest critical concentration. showed a higher temperature sensitivity than BHA. Therefore,
The possible reason is that the reaction mechanism of TBHQ the biodiesel stabilized with PY and BHA demonstrated a lower
with the free radicals is quite different from that of the other temperature dependence with respect to oxidation compared to
four compounds: TBHQ can act as not only a radical scavenger samples with TBHQ, PG, and BHT, because the latter
but also a radical producer.4 Given the fact that the oxidation displayed higher susceptibility to oxidative degradation at a
products of TBHQ may be also effective in retarding the higher temperature than the former.
oxidation, it would be difficult to determine when the critical 3.4. Shelf-Life Prediction. To verify the temperature
concentration is reached.25,26 Therefore, the prediction of the dependence of the induction period, Figure 4 shows the natural
antioxidant efficiency based only on the critical antioxidant logarithm of the induction period (ln IP) as a function of the
concentration can be misleading when the critical antioxidant temperature (in °C) for biodiesel stabilized with antioxidants. A
concentration does not take the antioxidative effects of the high linear relationship (R2 > 0.9963) exists between the
oxidation products into consideration. In the case of TBHQ, it decrease in the induction period with an increasing temper-
was assumed that the oxidation products formed during the ature. A 10 °C rise in the temperature decreased the induction
antioxidative process as well as the TBHQ itself contributed to period by a factor of 2.10−2.20 for TBHQ and PG, 2.11−2.19
the improvement of oxidation stability.25,26 for BHT, 2.02−2.17 for PY, and 1.98−2.13 for BHA. Both
The Arrhenius equation, k = A exp(−Ea/RT), was employed antioxidant type and antioxidant concentration affected the
to describe the temperature dependence of the reaction temperature coefficients. If the mechanism of antioxidant action
constant k, where A is the pre-exponential factor, Ea is the in biodiesel does not change at room temperature,31 the
apparent activation energy, R is the ideal gas law constant straight lines in Figure 4 could be extrapolated to ambient
(8.314 J mol−1 K−1), and T is the absolute temperature in temperature (25 °C) to obtain the shelf life of biodiesel, as
kelvin. In Figure 3, it can be seen that ln k versus 1/T (in K) shown in Figure 5.
follows a strong linear relationship over the whole temperature Apparently, TBHQ, PY, and PG presented a longer shelf life
range studied, with the coefficient of determination R2 being than BHA and BHT at ambient temperature. A half year of
0.9998, 0.9996, 1, 0.9993, and 0.9986 for THBQ, PY, PG, BHA, shelf life is now recommended for biodiesel under common
and BHT, respectively. The activation energy Ea for the market conditions.8,9,32 A total of 250 ppm of TBHQ, PG, PY,
BHT, and BHA could have a guarantee of approximately 25.0,
13.9, 13.2, 6.8, and 5.4 months of storage, respectively. The
extrapolated induction period of BHT at a lower temperature
was much higher than that of BHA, probably as a result of
lower volatilization and decomposition losses. At concen-
trations greater than 250 ppm, the shelf life of PY and BHA
seemed to be independent of the antioxidant concentration but
dependent upon the antioxidant type. Over the whole
concentration range, a longer shelf life would be expected
with a higher antioxidant concentration in the cases of TBHQ,
PG, and BHT. Overall, the shelf life for these antioxidants could
be ranked as follows: TBHQ > PG > PY > BHT > BHA,
basically in agreement with the order of the reaction constant of
antioxidant consumption. According to the results obtained, a
lower reaction rate of antioxidant consumption seemed to lead
to a longer shelf life of biodiesel.
It should be mentioned that the Rancimat method has rarely
been applied in realistic storage conditions to obtain the shelf
life of biodiesel. As pointed out by Reynhout,33 the Rancimat
method has its own limitations: long induction times may not
be accurately determined with this method as a result of water
Figure 3. Temperature dependence of the reaction constant for evaporation in the conductivity cells. According to Xin et al.,8
antioxidant consumption. the overall storage stability of biodiesel cannot be directly
F DOI: 10.1021/acs.energyfuels.6b02199
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Energy & Fuels Article

Figure 4. Natural logarithm of the Rancimat induction period as a function of the temperature (°C) for biodiesel stabilized with various
concentrations of antioxidants.

of peroxide values could be a valuable index to verify the

usefulness of the extrapolation fit of the Rancimat method. On
the basis of the induction period values determined at elevated
temperatures (70−110 °C) using the Rancimat apparatus,
Pereira et al.10 obtained an estimated shelf life of 186−376 days
at room temperature (15−25 °C) with the extrapolation
method, which agreed with the induction period value of 314
days, determined by monitoring the rate of hydroperoxide
formation. The only challenge with realistic shelf-life experi-
ments is that it could take months or years to obtain the
induction period values, which could explain why the shelf life
of biodiesel has been determined in most cases by the
extrapolation method.
3.5. Biodiesel Oxidation Kineitcs. The oxidation of
biodiesel generally proceeds according to the free-radical chain
reaction mechanism characterized by an induction period. A
pseudo-first-order reaction was often employed to simplify the
kinetics of biodiesel oxidation before the induction period.12,19
The temperature dependence of the induction period could be
Figure 5. Shelf life of biodiesel at ambient temperature stabilized with expressed with an Arrhenius-like equation: IP = A′ exp(Ea/RT).
antioxidants by the extrapolation method. According to Dunn,19 this model provides a means for
quantifying the kinetic parameters of the biodiesel oxidation
measured with the Rancimat method, because many factors reaction. As seen from Figure 6, a strong linear relationship (R2
could affect the fuel quality during storage, such as the presence > 0.9985) with a positive slope (Ea/R) could be observed
of water, microbial contamination, and storage conditions. On between the natural logarithm of the induction period (ln IP)
the basis of the assumption that the mechanism of the oxidation and the inverse of the temperature (1/T).
reaction does not change at high (above 100 °C) and low The addition of antioxidants in biodiesel presented different
(close to storage) temperatures, the extrapolation method, temperature dependences. The apparent activation energy Ea
widely used in many studies, could provide a useful practice for for the oxidation of biodiesel stabilized with antioxidants was
predicting the shelf life of biodiesel at low temperatures. shown in Figure 7. The untreated biodiesel reported an Ea of
To verify the extrapolated induction period determined by 99.18 kJ/mol, which could be increased to 103.74, 104.52,
the standard Rancimat method, realistic shelf-life experiments 106.21, and 100.52 kJ/mol for biodiesel treated with 100 ppm
are of great importance. In previous studies, the shelf life of of TBHQ, PY, PG, and BHT, respectively. A further increase in
biodiesel at low temperatures is often determined by the concentration led to a decrease in the activation energy for
monitoring the increase of primary oxidation products the oxidation of biodiesel, following an opposite trend than
(peroxide values) during the oxidative deterioration.12,13 The expected: higher concentrations generally give increased values
pioneering work by Pereira et al.10 convinced that the evolution of Ea. Of these antioxidants, PY and BHA showed the most
G DOI: 10.1021/acs.energyfuels.6b02199
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Energy & Fuels Article

Figure 6. Temperature dependence of the Rancimat induction period for biodiesel stabilized with various concentrations of antioxidants.

sensitivity of BHT, which demonstrated a higher protective

effect at a lower temperature than BHA. It should be
mentioned that these phenolic compounds, possibly acting as
prooxidants at higher concentrations, are more easily oxidized
than the biodiesel substrate during the antioxidative process.
Care must be taken when interpreting the apparent activation
energy for the oxidation of biodiesel: the participation of these
antioxidants in other side reactions, especially at higher
concentration levels, may change the course of the oxidation
reaction as well as the mechanism.17,34

4. CONCLUSION
Kinetic studies on the oxidation of biodiesel and the
consumption of antioxidants were performed in this work. An
increase in stability of biodiesel could be observed with the
addition of antioxidants. These antioxidants, differing in their
antioxidative characteristics, could be ranked in different orders
according to different parameters: antioxidant efficiency
Figure 7. Apparent activation energy for the oxidation of biodiesel (TBHQ > PY > PG > BHA > BHT), consumption rate
stabilized with antioxidants obtained from the Arrhenius-like equation. (TBHQ < PG < PY < BHA < BHT), critical concentration (PY
< PG < BHA < BHT < TBHQ), apparent activation energy
marked decrease of the activation energy with an increasing (TBHQ, PG > BHT > PY > BHA), and predicted shelf life
concentration. Further addition of PY and BHA to untreated (TBHQ > PG > PY > BHT > BHA).
biodiesel decreased the temperature dependence of the The lower consumption rate of antioxidant seemed to lead to
oxidation reaction to a large extent. Overall, the apparent a longer induction period and predicted shelf life of biodiesel.
activation energy Ea for the oxidation of biodiesel agreed The determination of the critical concentration would be
reasonably well with the order of Ea for the consumption of difficult when the oxidation products of the antioxidant
antioxidant: TBHQ, PG > BHT > PY > BHA. contributed to the improvement of oxidation stability. More
The oxidation of biodiesel stabilized with TBHQ, PG, and work is needed in the future to confirm the antioxidative effects
BHT was more temperature-sensitive than that with PY and of the oxidation products of TBHQ formed during the
BHA; increasing the temperature had more significant effects antioxidative process of biodiesel oxidation. Of these
on the oxidation of biodiesel treated with TBHQ, PG, and antioxidants, PY and BHA did not show an increase of
BHT than the latter. Although PY presented higher antioxidant projected shelf life but instead a marked decrease of activation
efficiency than PG at all test temperatures, the lower activation energy with an increasing concentration. The apparent
energy of PY than PG indicated that the latter was more activation energy Ea for the consumption of the antioxidant
susceptible to oxidative degradation at a higher temperature agreed well with the order of Ea for the oxidation of biodiesel;
than the former. The same held true for the higher temperature TBHQ, PG, and BHT, more temperature sensitive than PY and
H DOI: 10.1021/acs.energyfuels.6b02199
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Energy & Fuels Article

BHA, demonstrated higher susceptibility to oxidative degrada- oxidation stability of commercial biodiesel fuels. Fuel 2012, 93, 391−
tion at a higher temperature. 396.
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■ AUTHOR INFORMATION
Corresponding Author
Fuel 2016, 184, 808−814.
(18) Anwar, F.; Bhanger, M. I.; Kazi, T. G. Relationship between
rancimat and active oxygen method values at varying temperatures for
several oils and fats. J. Am. Oil Chem. Soc. 2003, 80, 151−155.
*E-mail: [email protected]. (19) Dunn, R. O. Effect of temperature on the oil stability index
ORCID (OSI) of biodiesel. Energy Fuels 2008, 22, 657−662.
Jian Zhou: 0000-0001-9357-2929 (20) Zhou, J.; Xiong, Y.; Liu, X. Evaluation of the oxidation stability
of biodiesel stabilized with antioxidants using the Rancimat and PDSC
Notes methods. Fuel 2017, 188, 61−68.
The authors declare no competing financial interest. (21) Tang, H.; Wang, A.; Salley, S. O.; Ng, K. S. The effect of natural

■
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I DOI: 10.1021/acs.energyfuels.6b02199
Energy Fuels XXXX, XXX, XXX−XXX