Fuel 232 (2018) 108–113

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Fuel
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Full Length Article

Rancimat and PetroOxy oxidation stability measurements of rapeseed oil T

methyl ester stabilized with hydrazides and antioxidants
⁎
Ferdinand Bära, , Henning Hopfb, Markus Knorra, Jürgen Krahlc,d
a
Coburg University of Applied Sciences and Arts, Coburg, Germany
b
Technical University of Braunschweig, Germany
c
OWL University of Applied Sciences, Lemgo, Germany
d
Fuels Joint Research Group, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: Fossil fuels are still one of the world’s major sources of energy. Because of their reduced availability in the future,
Biodiesel however, renewable resources like biodiesel provide an attractive substitute to meet the growing demand for
Additives energy supply. Significant problems associated with the use of biodiesel are low its oxidation stability and a
Antioxidants higher NOx emission tendency. It was shown by Bär et al. (2017) [1] that 2,4,6-tris-isopropylbenzoic acid hy-
Oxidation stability
drazide and benzoic hydrazide can act as antioxidants in distilled biodiesel. Simultaneously, hydrazides showed
Hydrazides
the potential to lower NOx emissions [2]. In this context, 14 additional hydrazides and four phenolic anti-
oxidants were tested for their antioxidant properties by using the Rancimat method (DIN EN 15751) and
PetroOxy method (DIN EN 16091). All hydrazides were employed at a concentration of 7.26 mmol/kg, which
corresponds to approximately 1000 ppm of benzoic hydrazide. It is shown that all hydrazides increase the
oxidation stability. The Rancimat tests verified that m-anisic hydrazide was most effective and extended the
induction period by 16.0 h, whereas isonicotinic hydrazide showed a maximum induction period extension of
24.47 min in the PetroOxy tests. Differences in measurement principles, temperatures and oxygen partial
pressures of both methods might explain the varying result. However, the phenolic antioxidant 2,2′-methyle-
nebis(6-tert-butyl-4-methyl-phenol) increased the induction period from 3.7 h for neat RME to a maximum of
21.2 h in the Rancimat test and from 16.18 min to a maximum of 71.91 min in the PetroOxy test.

1. Introduction rail injection systems, a number of other theories were developed. It is

Despite many advantages of biodiesel like renewability, high lu-
bricity and reduced emissions of carbon monoxide (CO), unburned
hydrocarbons (HC) and particulate matter (PM) compared to fossil
diesel fuel, biodiesel tends to increase NOx emissions and has a poor
oxidation stability.
A common theory for the higher NOx emissions of biodiesel in
pump-line-nozzle fuel injection systems contributes with speed of sound
and bulk modulus of compressibility of biodiesel and fossil diesel fuel.
Biodiesel is less compressible than fossil fuel, which leads to premature
fuel injection. This results in a higher peak in-cylinder temperature and
increasing thermal NOx formation [3–5]. However, Cheng et al. [6]
showed that a fixed start of combustion timing leads to a load-averaged
NOx increase of about 10% for soy-based biodiesel relative to fossil
diesel fuel.
Due to the fact that bulk-modulus effect cannot occur in common
known that biodiesel combustion produces less soot than the combus-
tion of fossil diesel fuel. Mueller et al. [7] and Cheng et al. [6] in-
vestigated the radiative heat transfer of soot particles within the com-
bustion chamber and found evidence that higher soot emissions from
fossil diesel fuel combustion lower the combustion temperature by ra-
diative heat transfer and therefore produces less thermal NOx compared
to the combustion of biodiesel. Another theory presented by Hoekman
and Robbins [8] postulate that the higher cetane number of biodiesel
causes a shorter ignition delay and therefore a longer residence time at
elevated temperature. However, this theory is in contrast to results of
McCormick et al. [9], who reduced NOx emissions by cetane number
enhancers. They concluded that a higher cetane number leads to less
premixed air/fuel-mixture at the moment of combustion and that this
could lead to a lower peak in-cylinder temperature.
Various studies showed that additives can mitigate NOx emissions
from biodiesel and biodiesel blends [9–14]. Krahl et al. [2]

⁎
Corresponding author.
E-mail address: ferdinand.baer@tac-coburg.de (F. Bär).
URL: https://www.fuels-jrg.de (J. Krahl).

https://doi.org/10.1016/j.fuel.2018.05.095
Received 8 January 2018; Received in revised form 30 April 2018; Accepted 18 May 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
F. Bär et al. Fuel 232 (2018) 108–113

demonstrated that 2000 ppm of cis-9-octadecenoic hydrazide in com-

bination with a solubilizer reduces NOx emissions from biodiesel com-
busted in an ignition bomb to ca. 45%. Bär and Krahl [15,16] showed
that under optimized pressure and temperature conditions a slight de-
crease of NOx emissions from ignition bomb tests can be found by
adding 1000 ppm benzoic hydrazide into rapeseed oil methyl ester. Fig. 1. Antioxidative action of hydrazides.
The poor oxidation stability of biodiesel is caused by unsaturated
and polyunsaturated compounds like oleic acid methyl ester (C18:1), Rancimat and the PetroOxy method.
linoleic acid methyl ester (C18:2) and linolenic acid methyl ester
(C18:3). Those compounds tend to abstract allylic and bis-allylic hy-
2. Experimental details
drogen radicals, initiating a classical free radical chain reaction me-
chanism (autoxidation) [17]:
2.1. Additives
RH →R%+H%
The additives used in the present study are shown in Table 1. Pivalic
R%+O2→ROO% hydrazide was synthesized according to Bär et al. [22]. 2,4,6-tris-iso-
ROO% + RH→ROOG+R% propylbenzoic hydrazide was synthesized according to Bär et al. [1]. All
other additives were either purchased by Alfa Aesar, Merck, Lanxess or
R% R% →RR Sigma Aldrich (for synthesis).
ROO% R% →stable products The additives were compared either in constant mass concentration
or constant molar concentration. A comparison of mass concentrations
The formation of reaction products is a multi-step process where is the more technical approach, whereas a comparison of molar con-
primary oxidation products like hydroperoxides and epoxides decom- centrations gives a better scientific understanding of the effectiveness of
pose, interact with each other and form stable secondary oxidation the additives. BHT is a commonly used antioxidant in biodiesel and
products such as aldehydes, aliphatic alcohols, formic acid, formate therefore it was used as a reference.
esters, shorter chain fatty acids and oligomers with molecular weights
up to 1600 g/mol [17,18]. The resulting oxidation products can lead to 2.2. Fuels
higher emissions, a higher corrosiveness, fuel filter blocking, clogging
of fuel injectors, the formation of deposits in the fuel system and a Following the common nomenclature, the amount of biodiesel
decreasing lubricity [19]. added to conventional fossil diesel fuel determines the blend name (e.g.
To prevent those effects, diesel fuel contains oxidation inhibitors 7% biodiesel = B7)
(antioxidants). Beside natural antioxidants a number of highly effective The B100 used was made of rapeseed oil, which gives rapeseed oil
synthetic antioxidants have been developed. In general, antioxidants methyl ester (RME) purchased from ASG – Analytik Service
can be classified as hydroperoxide decomposers or radical scavengers, Gesellschaft.
which break the chain reaction of autoxidation. However, antioxidants Distilled rapeseed oil methyl ester contains no natural antioxidants
are consumed in this process, resulting in partial loss of their efficiency and therefore it was used to prevent interactions between natural and
against oxidative stress during an induction period. synthetic antioxidants. The distilled RME was obtained from ASG –
Phenolic and aminic antioxidants break the chain reaction by ab- Analytik Service Gesellschaft.
stracting hydrogen radicals. These hydrogen radicals react with radicals The fossil diesel fuel was delivered from remaining stock of the
from autoxidation and form stable products. The resulting antioxidant Thünen Institut Braunschweig.
radical is either stable or further engages in a reaction to form stable
molecules. Hydroperoxide decomposers, convert hydroperoxides into
2.3. Methods
non-radical, non-reactive, and thermally stable products.
Since oxidative stability significantly affects fuel quality, a number
The oxidation stability tests with benzoic hydrazide, 2,4,6-tris-iso-
of oxidation stability determination methods have been developed. The
propylbenzoic hydrazide and BHT in distilled RME were done in tri-
standardized accelerated oxidation stability test method accepted in
plicate. Results are presented as mean values and standard deviations of
DIN EN 590 and DIN EN 14214 is the Rancimat test (DIN EN 15751 and
three replicates.
DIN EN 14112). A more rapid test to determine oxidation stability of
All other oxidation stability tests were performed as single de-
fuels called PetroOxy test was reported by Neumann et al. [20] (DIN EN
termination.
16091). Both methods determine a so-called induction time, which can
A statistically different significance was accepted for a 95% con-
be correlated to the oxidation stability.
fidence interval which reflects a significance level of P < .05.
The European standard DIN EN 14214 sets a lower limit of 8 h for
Oxidation stability was determined by the Rancimat method
neat biodiesel as the minimum induction period determined by the
(Metrohm Biodiesel Rancimat 873) according to DIN EN 15751 and by
Rancimat method. DIN EN 590 defines a limit of 20 h for fuel blends
the PetroOxy method (Petrotest PetroOxy) according to DIN EN 16091.
with up to 7% (V/V) biodiesel content. Minimum values for induction
The Rancimat method was first proposed by Hadorn and Zurcher
periods determined by PetroOxy have yet to be defined for European
[23]. The accelerated oxidation test is carried out by heating a sample
standards.
to 110 °C in a sealed test tube while passing an air flow through it.
Bär et al. [1] reported that 2,4,6-tris-isopropylbenzoic acid hy-
Volatile oxidation products such as acetic acid and formic acid are
drazide and benzoic hydrazide can act as antioxidants in biodiesel.
dragged by the air flow into a vessel filled with distilled water. The
Timmins and Deretic [21] reported that hydrazides can abstract hy-
conductivity of the aqueous phase is monitored and due to the ap-
drogen atoms from the hydrazide group breaking the chain reaction of
pearance of the oxidation products in the water a significant change of
autoxidation (Fig. 1). Simultaneously, hydrazides showed the potential
conductivity can be detected when the aging process has started. The
for NOx emission reduction [2,15,16].
oxidation stability can be correlated to the so-called induction time
In this context, the main goal of this paper is to compare the oxi-
elapsed from the start of the test until secondary oxidation products
dation behavior of biodiesel treated with various hydrazides and
increase the conductivity in the water cell.
common antioxidants. Oxidation stabilities were measured by the
The PetroOxy method was originally presented by Neumann et al.

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F. Bär et al. Fuel 232 (2018) 108–113

Table 1
Structural formulas of tested additives.

[20]. In a hermetically sealed test chamber 5 ml of a sample are pres- second. The test ends when a pressure drop of 10% from maximum
surized with oxygen at 700 kPa and then heated to 140 °C. Due to the pressure is reached and the time that passed determines the induction
heating the pressure increases to a maximum. The oxygen is consumed time.
during the aging process and the pressure drop is recorded every

110
F. Bär et al. Fuel 232 (2018) 108–113

Table 2 Table 4
Oxidation stability test results for various concentrations of RME in fossil diesel Oxidation stability test results for various concentrations of propyl gallate (PG)
fuel. and pyrogallol (PY) in distilled RME.
Sample DIN EN 15751 [h] DIN EN 16091 [min] Sample DIN EN 15751 [h] DIN EN 16091 [min]

*
B0 Not applicable 95.00 Neat distilled RME 0 8.08 ( ± 0.4)
B2 31.9 80.96 PG 125 ppm 13.3 24.17
B7 26.5 43.56 PG 250 ppm 13.5 26.45
B10 20.8 32.48 PG 500 ppm 16.3 32.19
B20 14.4 23.58 PG 1000 ppm 17.9 36.74
B50 7.9 15.16 PY 375 ppm 13.6 13.65
B100 3.7 16.18 PY 500 ppm 17.0 20.54
PY 750 ppm 22.0 29.17
* According to DIN EN 15751 the oxidation stability of diesel fuel with less PY 1000 ppm 23.0 40.72
than 2% (V/V) of biodiesel cannot be determined by Rancimat method. BHT 500 ppm 4.9 9.03
BHT 1000 ppm 8.9 21.00

35 120
Rancimat induction period

PetroOxy induction period

Rancimat
30 100 isopropylbenzoic hydrazide and benzoic hydrazide, although all ad-
PetroOxy
25 ditives increased the induction period. Neat distilled RME contains no
80 antioxidants and therefore it has no oxidation stability. The con-
20
[min]
[h]

60 ductivity measured by Rancimat increases without any induction period

15
40
10
5 20
0 0
0 10 20 30 40 50 60 70 80 90 100
biodiesel content [% (V/V)]
Fig. 2. Rancimat and PetroOxy induction periods for various RME concentra-
tions in fossil diesel fuel.
3. Oxidation stability test results
In a first series of measurements the effect of addition of RME to
fossil diesel fuel was investigated (Table 2 and Fig. 2) to point out the
relevance of antioxidants when biodiesel is used as a blend component
or as neat fuel.
It can be shown that even small amounts (> 5% (V/V)) of RME
lower the induction period drastically (Fig. 2) and that the addition of
highly effective antioxidants is strongly recommended to guarantee
long-term storage stability.
In a series of further investigations, the effect of potential anti-
oxidants was determined.
It is known that synergistic or antagonistic interactions between
antioxidants can influence the effectiveness of oxidation inhibition
[24–27]. Biodiesel can contain natural antioxidants like tocopherols
and carotenoids. These antioxidants can be removed by distillation. To
prevent interactions between natural antioxidants and the synthetic
additives, measurements with distilled RME were performed (Table 3).
An additive concentration of 4.5 mmol/kg was chosen for BHT, benzoic
hydrazide and 2,4,6-tris-isopropylbenzoic hydrazide. This concentra-
tion corresponds to approximately 1000 ppm BHT which is the re-
commended minimum BHT concentration in biodiesel according to DIN
EN 14214. As indicated by Rancimat tests, the PetroOxy measurements
proved BHT to be the more effective antioxidant compared to 2,4,6-tris-
Table 3
Oxidation stability test results for various additives in a concentration of
4.5 mmol/kg in distilled RME.
which is represented by a value of zero hours.
A number of studies point out that pyrogallol and propyl gallate are
highly effective antioxidants in different kinds of biodiesel [24,28–30].
Due to the fact that the concentration of natural antioxidants in the
mentioned studies is not known and possible synergistic effects between
natural and synthetic antioxidants were not investigated, tests were
carried out using various concentrations of pyrogallol, propyl gallate
and BHT in distilled RME (Table 4). The results indicate that pyrogallol,
propyl gallate increase the oxidation stability more effectively than
BHT at a concentration of 500 ppm and 1000 ppm, regardless of whe-
ther PetroOxy or Rancimat was used in the oxidation stability de-
termination. In addition, both antioxidants increase the oxidation sta-
bility more effectively than benzoic hydrazide at a concentration of
613 ppm (4.5 mmol/kg).
Taking into account that the usage of distilled biodiesel is highly
unfavorable, tests with common antioxidants and a number of hy-
drazides in conventional RME were performed (Tables 5 and 6).
The tests with various concentrations of BHT and benzoic hydrazide
showed that both additives increase the oxidation stability (Table 5).
BHT was found to be more effective, although the molar concentration
of benzoic hydrazide was 1.6 times higher than the molar concentration
of BHT.
The results of the oxidation stability tests with an additive con-
centration of 7.26 mmol/kg are shown in Table 6. The concentration of
7.26 mmol/kg corresponds to approximately 1000 ppm of benzoic hy-
drazide.
Due to the tendency of hydrazides to form strong hydrogen bonds
[31,32], they display a poor solubility in biodiesel, biodiesel blends or
fossil diesel fuels at room temperature. However, all hydrazides tested
are soluble at the concentrations used and at the specified temperature
of measurement (110 °C (DIN EN 15751) and 140 °C (DIN EN 16091).
Hydrazides which are not soluble at the concentrations tested and at
25 °C are marked with an asterisk in Table 6. To find out whether the
Table 5
Oxidation stability test results for various concentrations of BHT and benzoic
hydrazide (BH) in RME.
Sample DIN EN 15751 [h] DIN EN 16091 [min]

Sample DIN EN 15751 [h] DIN EN 16091 [min] Neat RME 3.7 16.18
BHT 500 ppm 6.4 26.61
Neat distilled RME 0 8.08 ( ± 0.4) BHT 1000 ppm 8.5 35.61
2,4,6-tris-isopropylbenzoic 2.3 ( ± 0.1) 10.25 ( ± 0.8) BHT 1500 ppm 10.2 44.41
hydrazide BH 500 ppm 5.1 19.63
Benzoic hydrazide 1.7 ( ± 0.1) 9.51 ( ± 0.5) BH 1000 ppm 7.1 22.90
BHT 6.2 ( ± 0.3) 23.01 ( ± 0.5) BH 1500 ppm 8.9 25.33

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F. Bär et al. Fuel 232 (2018) 108–113

Table 6 antioxidants in biodiesel and hydrazides simultaneously show the po-

Oxidation stability test results for various additives in a concentration of tential for NOx emission reduction [2], 14 additional hydrazides were
7.26 mmol/kg in RME. tested for their antioxidant properties in the same molar concentration
Sample DIN EN 15751 DIN EN 16091 (7.26 mmol/kg).
[h] [min] All hydrazides tested increased the Rancimat induction time, al-
though the limit of solubility was exceeded for some of the hydrazides
Neat RME 3.7 16.18
at 25 °C. However, at the temperature of measurement (110 °C (DIN EN
BHT 15.2 56.18
2,2′-methylenebis(6-tert-butyl-4- 21.2 71.91 15751) and 140 °C (DIN EN 16091)) all hydrazides investigated can be
methylphenol)* dissolved in RME.
Benzoic Hydrazide 15.8 35.73 In relation to the commonly used antioxidant BHT, five hydrazides
Acetic hydrazide * 7.0 29.35
showed a comparable performance in the Rancimat tests. m-Anisic
Pivalic hydrazide 7.6 30.78
Phenylacetic hydrazide 10.6 27.51
hydrazide performed best and increased the induction period from 3.7 h
2-furoic hydrazide 12.2 37.90 for neat RME to 19.7 h.
Isonicotinic hydrazide 16.5 40.65 However, 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol) in-
Adipic dihydrazide * 7.5 28.61 creased the induction period to a maximum of 21.2 h.
p-toluic hydrazide * 16.0 36.31
The PetroOxy tests presented a different picture. Isonicotinic hy-
n-butyric hydrazide * 6.0 22.70
Vanillic hydrazide * 17.9 46.95 drazide showed the highest increase of oxidation stability and improved
(3,4-dimethoxyphenyl)- acetic hydrazide *
11.8 30.90 the induction period from 16.18 min to 40.65 min. m-Anisic hydrazide
m-anisic hydrazide 19.7 37.40 extended the induction period to 37.40 min.
boc-glycine hydrazide * 8.0 24.15
The overall analysis of the results from Rancimat and PetroOxy tests
Biphenyl-4-carboxylic hydrazide * 13.3 26.93
Isobutyric hydrazide * 6.2 25.78
revealed significant differences in the effectiveness of the hydrazides.
2,4,6-tris-isopropylbenzoic hydrazide 9.5 35.93 The performance of antioxidants is highly dependent on the conditions
of oxidation [35–38]. Therefore, the different measurement principles,
* Solubility limit exceeded at 25 °C. temperatures and oxygen partial pressures of both methods might ex-
plain the varying results. Based on the available data, however, it
search for solubilizers is desirable, the tests were also carried out when cannot be verified which of the two methods provides a better esti-
the solubility limit at 25 °C was exceeded. mation of the effectiveness of hydrazides in fuel. Long-term storage
The most effective hydrazide was m-anisic hydrazide. It increased experiments under realistic aging conditions should be performed to
the induction period by 16 h in the Rancimat test. BHT increased the determine the most effective hydrazide additive.
induction period by 11.5 h. Furthermore, benzoic hydrazide, p-toluic
hydrazide, vanillic hydrazide and isonicotinic hydrazide showed nearly References
the same oxidation stabilizing potential as BHT.
The PetroOxy tests showed a number of differences compared to the [1] Bär F, Hopf H, Knorr M, Krahl J. Synthesis, characterization and antioxidant
Rancimat measurements. In this series of tests the most effective hy- properties of 2,4,6-tris-isopropylbenzoic acid hydrazide in biodiesel. Fuel
2017;215:249–57.
drazide was isonicotinic hydrazide. It increased the induction period by
[2] Krahl J, Tanugula S, Hopf H. Diesel Fuel Additives to Reduce NOx Emissions from
24.47 min. However, BHT increased the induction period by 34.00 min. Diesel Engines Operated on Diesel and Biodiesel Fuels by SNCR. SAE International
In contrast to the Rancimat tests, m-anisic hydrazide showed a much 2010–01-2280 2010(2010–01-2280).
lower efficiency than BHT. [3] Szybist JP, Kirby SR, Boehman AL. NOx emissions of alternative diesel fuels: a
comparative analysis of biodiesel and FT diesel. Energy Fuels 2005;19(4):1484–92.
The commonly used antioxidant 2,2′-methylenebis(6-tert-butyl-4- [4] Tat ME, Van Gerpen JH. Measurement of biodiesel speed of sound and its impact on
methylphenol) exhibited the highest increase of oxidation stability in injection timing. Nat Renewable Energy Labor 2003. NREL/SR-510-31462.
the Rancimat and PetroOxy tests. [5] Ye P, Boehman AL. Investigation of the impact of engine injection strategy on the
biodiesel NOx effect with a common-rail turbocharged direct injection diesel engine.
Depending on the method of measurement, the overall analysis of Energy Fuels 2010;24(8):4215–25.
the results showed significant differences in the oxidation stabilizing [6] Cheng AS, Upatnieks A, Mueller CJ. Investigation of the impact of biodiesel fuelling
potential of the tested additives. The deviations might be related to the on NOx emissions using an optical direct injection diesel engine. Int J Engine Res
2006;7(4):297–318.
different accelerated fuel aging conditions. Rancimat detects highly [7] Mueller CJ, Boehman AL, Martin GC. An Experimental Investigation of the Origin of
volatile oxidation products like carboxylic acids [33] by a combination Increased NO x Emissions When Fueling a Heavy-Duty Compression-Ignition Engine
of distillation and conductivity measurement. The vaporized products with Soy Biodiesel. SAE Int 2009.
[8] Hoekman SK, Robbins C. Review of the effects of biodiesel on NOx emissions. Fuel
can no longer participate in the reaction, whereas the PetroOxy method
Process Technol 2012;96:237–49.
includes all volatile and non-volatile oxidation products [34]. A number [9] McCormick RL, Alvarez JR, Graboski MS. NOx Solutions for Biodiesel: Final Report
of studies showed that oxidation conditions such as temperature and Report 6 in a series of 6. Nat Renewable Energy Labor 2003. NREL/SR-510-31465.
[10] Varatharajan K, Cheralathan M. Effect of aromatic amine antioxidants on NOx
oxygen partial pressure have a substantial impact on the efficiency of
emissions from a soybean biodiesel powered DI diesel engine. Fuel Process Technol
antioxidants [35–38]. Thus, based on the available data it cannot be 2013;106:526–32.
determined which of the two methods of measurement provide a better [11] Varatharajan K, Cheralathan M, Velraj R. Mitigation of NOx emissions from a ja-
estimation of the effectiveness of the antioxidants in fuel. Therefore, tropha biodiesel fuelled DI diesel engine using antioxidant additives. Fuel Proc.
Tech. 2011;90:2721–5.
long-term storage experiments under realistic storage conditions will [12] İleri E, Koçar G. Effects of antioxidant additives on engine performance and exhaust
have to be performed e.g. in fuel tanks [39,40]. emissions of a diesel engine fueled with canola oil methyl ester-diesel blend. Energy
Convers Manage 2013;76:145–54.
[13] İleri E, Koçar G. Experimental investigation of the effect of antioxidant additives on
4. Summary NOx emissions of a diesel engine using biodiesel. Fuel 2014;125:44–9.
[14] Rizwanul Fattah IM, Masjuki HH, Kalam MA, Mofijur M, Abedin MJ. Effect of an-
tioxidant on the performance and emission characteristics of a diesel engine fueled
Tests with various concentrations of rapeseed oil methyl ester in
with palm biodiesel blends. Energy Convers Manage 2014;79:265–72.
fossil diesel fuel indicate that even small proportions of biodiesel [15] Bär F, Krahl J. Schaffung eines Kraftstoffs mit geringem NO2-Ausstoß und hohem
(> 5% (V/V)) can lower the oxidation stability drastically. Therefore, Biogenitätsgehalt (Development of a diesel fuel with low NO2 emission and high
DIN EN 14214 recommends the usage of an antioxidant equivalent of biocontent); Umweltforschungsdatenbank UFORDAT Nr.: 01034854.
Abschlussbericht zum Forschungsvorhaben (Report) 2013.
1000 ppm BHT for biodiesel stabilization. [16] Bär F, Krahl J. Schaffung eines biodieselbasierten Kraftstoffs mit geringem NO2-
Due to the fact that Bär et al. [1] reported that 2,4,6-tris-iso- Ausstoß und hoher Oxidationsstabilität (Creation of a biodiesel based fuel with low
propylbenzoic acid hydrazide and benzoic hydrazide can act as NO2 emission and high oxidation stability). Abschlussbericht zum

112
F. Bär et al. Fuel 232 (2018) 108–113

Forschungsvorhaben (Report) 2014. (http://www.ufop.de/files/7914/2139/9745/
RZ_UFOP_1263_Schriften_Biodiesel_web.pdf).
[17] Flitsch S, Neu PM, Schober S, Kienzl N, Ullmann J, Mittelbach M. Quantitation of
aging products formed in biodiesel during the rancimat accelerated oxidation test.
Energy Fuels 2014;28(9):5849–56.
[18] Eskiner M, Bär F, Rossner M, Munack A, Krahl J. Determining the aging degree of
domestic heating oil blended with biodiesel by means of dielectric spectroscopy.
Fuel 2015;143:327–33.
[19] Kumar N. Oxidative stability of biodiesel: Causes, effects and prevention. Fuel
2017;190:328–50.
[20] Neumann A, Jebsen T, Wierzbicki V. A method for determining oxidation stability
of petrodiesel, biodiesel, and blended fuels. Am Lab 2008;40:20–6.
[21] Timmins GS, Deretic V. Mechanisms of action of isoniazid. Mol Microbiol
2006;62(5):1220–7.
[22] Bär F, Hopf H, Knorr M, Schröder O, Krahl J. Effect of hydrazides as fuel additives
for biodiesel and biodiesel blends on NOx formation. Fuel 2016;180:278–83.
[23] Hadorn H, Zürcher K. Bestimmung der oxidationsstabilität von Ölen und fetten.
Deutsche Lebensmittel Rundschau 1974;70:57–65.
[24] Rawat DS, Joshi G, Lamba BY, Tiwari AK, Kumar P. The effect of binary antioxidant
proportions on antioxidant synergy and oxidation stability of Jatropha and Karanja
biodiesels. Energy 2015;84:643–55.
[25] Prieto MA, Murado MA, Vázquez JA. Quantification, characterization and de-
scription of synergy and antagonism in the antioxidant response. Food Res Int
2014;60:218–29.
[26] Belitz H-D, Grosch W, Schieberle P. Lehrbuch der Lebensmittelchemie. 6th ed.
Berlin [u.a.]: Springer; 2008.
[27] Hajimehdipoor H, Shahrestani R, Shekarchi M. Investigating the synergistic anti-
oxidant effects of some flavonoid and phenolic compounds. Res J Pharmacog (RJP)
2014;3(1):35–40.
[28] Mittelbach M, Schober S. The influence of antioxidants on the oxidation stability of
biodiesel. J Am Oil Chem Soc 2003;80(8):817–23.
[29] Das LM, Bora DK, Pradhan S, Naik MK, Naik SN. Long-term storage stability of
biodiesel produced from Karanja oil. Fuel 2009;88(11). 2315–238.
[30] Obadiah A, Kannan R, Ramasubbu A, Kumar SV. Studies on the effect of anti-
oxidants on the long-term storage and oxidation stability of Pongamia pinnata (L.)
Pierre biodiesel. Fuel Process Technol 2012;99:56–63.
[31] Zhang H-H, Yuqing W, Lai B-L, Li M. Classification of the hydrogen-bonding species
in a series of novel hydrazide based azobenzene derivatives investigated by two-
dimensional correlation infrared spectroscopy and molecular modeling.
Spectrochimica Acta Part A 2006;63:117–25.
[32] Zabicky J. The Chemistry of Amides. London, New York: Interscience; 1970.
[33] de Carvalho AL, Cardoso EA, da Rocha GO, Teixeira LSG, Pepe IM, Grosjean DM.
Carboxylic acid emissions from soybean biodiesel oxidation in the EN14112
(Rancimat) stability test. Fuel 2016;173:29–36.
[34] Botella L, Bimbela F, Martín L, Arauzo J, Sánchez JL. Oxidation stability of biodiesel
fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-
dimethoxyphenol and catechol as biodiesel additives on oxidation stability. Front
Chem 2014(2):1–4.
[35] Burton GW. Antioxidant Action of Carotenoids. J Nurt 1989;1989(119):109–11.
[36] Brewer MS. Natural antioxidants: sources, compounds, mechanisms of action, and
potential applications. Compr Rev Food Sci Food Saf 2011;10(4):221–47.
[37] Linden S. α-Tocopherol, β -Carotin und L-Ascorbinsäure in der Rindermast.
Dissertation. Hamburg. 2003.
[38] Réblová Z. The effect of temperature on the antioxidant activity of tocopherols. Eur
J Lipid Sci Technol 2006;108(10):858–63.
[39] Thompson MR, Mu B, Ewaschuk CM, Cai Y, Oxby KJ, Vlachopoulos J. Long term
storage of biodiesel/petrol diesel blends in polyethylene fuel tanks. Fuel
2013;108:771–9.
[40] Karavalakis G, Hilari D, Givalou L, Karonis D, Stournas S. Storage stability and
ageing effect of biodiesel blends treated with different antioxidants. Energy
2011;36(1):369–74.

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