Fuel
journal homepage: www.elsevier.com/locate/fuel
a r t i c l e i n f o a b s t r a c t
Article history: Biodiesel is an alternative fuel derived from vegetable oils, animal fats and used frying oils. Due to its
Received 28 July 2009 chemical structure, it is more susceptible to oxidation or autoxidation during long-term storage com-
Received in revised form 23 March 2010 pared to petroleum diesel fuel. One of the major technical issues regarding the biodiesel blends with die-
Accepted 25 March 2010
sel fuel is the oxidation stability of the final blend, which is, nowadays, of particularly high concern due to
Available online 4 April 2010
the introduction of ultra low sulphur diesel, in most parts of the EU. This study examined the factors
influencing the stability of several biodiesel blends with low and ultra low sulphur automotive diesel
Keywords:
fuels. The aim of this paper was to evaluate the impact of biodiesel source material and biodiesel concen-
Biodiesel
Oxidation stability
tration in diesel fuel, on the stability of the final blend. Moreover, the effects of certain characteristics of
Diesel fuel the base diesels, such as sulphur content and the presence of cracked stocks, on the oxidation stability are
Rancimat method discussed.
Ó 2010 Elsevier Ltd. All rights reserved.
0016-2361/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.03.041
2484 G. Karavalakis et al. / Fuel 89 (2010) 2483–2489
apparatus is the test method for determining oxidative stability of tributors and biorefineries nationwide. The FAME samples were
biodiesel at 110 °C, with a minimum induction period of 6 h. How- used to create 168 blends at proportions of 2%, 3%, 4%, 5%, 75
ever, in order to ensure a high quality biodiesel within the EU, the and 10% by volume with the base diesel fuels. These blend propor-
CEN already discusses a limit change of a minimum induction per- tions were chosen as being representative of the currently mar-
iod of 8 h instead of 6 h. keted automotive diesel composition in Greece. The 7% blend
This work is important because it substantially increases was chosen since the EN 590:2009 includes a provision for diesel
knowledge on the oxidative behavior of the finished blend of bio- fuel to be blended with biodiesel up to 7% v/v. The 10% blend
diesel with petrodiesel using the modified Rancimat method. To was used since it is expected that the mixing ratio within the EU
the authors’ best knowledge, this is one of the first studies investi- to rise up to 10%. The neat biodiesels were examined according
gating a novel topic regarding the stability behavior of diesel–bio- to the automotive FAME standard EN 14214, published by the
diesel blends. The purpose of this study was to provide European Standard Organization (CEN) that establishes specifica-
experimental results on the effect of biodiesel concentration in die- tions for biodiesel use as a blendstock for conventional diesel fuel.
sel fuel along with the effects of certain physicochemical parame- The main properties of the biodiesels and the test methods used
ters. Furthermore, the impact of biodiesel source material on the are shown in Tables 2 and 3.
oxidation stability of the final blends was investigated. The properties of the four base diesel fuels fulfilled the Euro-
pean standard specifications of EN 590. D-1 and D-2 were charac-
terized by high polyaromatics content compared to D-3 and D-4.
2. Experimental The D-3 sample was of summer grade as indicated by the CFPP
analysis. Most of the physicochemical parameters of the methyl es-
2.1. Fuels ters were found to agree with the EN 14214 specifications. How-
ever, three biodiesel samples failed for oxidation stability, water
Four commercial automotive diesel fuels were selected as the content and iodine number and one sample failed for ester content
base fuels (D-1, D-2, D-3 and D-4). The first two samples were of and acid number. B-1, B-2, B-3 and B-7 samples were known not to
low sulphur (up to 50 ppm sulphur content) and the second two contain antioxidant additives. It was assumed that the saturated B-
samples were of ultra low sulphur (up to 10 ppm sulphur content). 4 and B-9 were free of antioxidants, while B-5, B-6 and B-8 were
D-2 and D-3 were hydrotreated straight run atmospheric gasoils, treated with phenolic-based antioxidant additives.
while D-1 and D-4 included streams from cracking processes as
middle distillate fuel extenders. The main properties of the base 2.2. Methyl esters fatty acid composition
diesel fuels are listed in Table 1.
Nine different types of commercially available FAMEs were also Information data on the raw materials used for the production
employed in this study. These biodiesels were collected from dis- of the biodiesel samples employed in this study were not available
Table 1
Properties of the base diesel fuels.
Table 2
Main physicochemical properties of the methyl esters (B-1, B-2, B-3, B-4 and B-5).
Property B-1 B-2 B-3 B-4 B-5 EN 14214 limits Test method
Viscosity (mm2/s, 40 °C) 4.4 4.5 4.6 3.6 4.25 3.50–5.00 EN ISO 3104
Density (g/cm3, 15 °C) 0.884 0.8839 0.8847 0.8763 0.8831 0.860–0.900 EN ISO 3675
Water content (lg g 1) 352 356 300 270 630 500 max EN ISO 12937
Cold filter plugging point, CFPP (°C) 2 1 10 2 1 +5 max EN 116
Iodine number 123 109 115 42 115 120 max EN 14111
Acid value (mgKOH/g) 0.14 0.11 0.14 0.32 0.38 0.50 max EN 14104
Oxidation stability (110 °C, h) 3.51 5.72 6.59 17.38 7.99 6 h min EN 14112
Monoglyceride content (% m/m) 0.33 0.22 0.32 0.57 0.44 0.80 max EN 14105
Diglyceride content (% m/m) 0.094 0.05 0.052 0.08 0.04 0.20 max EN 14105
Triglyceride content (% m/m) 0.08 0.086 0.083 0.02 0.088 0.20max EN 14105
Total glycerol (% m/m) 0.111 0.076 0.105 0.150 0.131 0.25 max EN 14105
Ester content (% m/m) 95.9 97.8 97.9 98.4 97.9 96.5 min EN 14103
Linolenic acid methyl ester (% m/m) 3.3 3.1 4.4 0.12 4.67 12 max EN 14103
G. Karavalakis et al. / Fuel 89 (2010) 2483–2489 2485
Table 3
Main physicochemical properties of the methyl esters (B-6, B-7, B-8 and B-9).
except for B-1, B-2, B-3 and B-7. The feedstocks used for the pro- 3. Results and discussion
duction of B-1 were 65% refined rapeseed oil and 35% used frying
oils. B-2 derived from 36% used frying oils, 20% palm oil and 44% 3.1. Oxidation stability of biodiesel samples
soybean oil, while B-3 feedstocks were 32% used frying oils, 32%
soybean oil and 36% rapeseed oil. B-7 was produced from pure ra- Fig. 1 shows the changes recorded on the oxidation stability of
peseed oil. Table 4 shows the main fatty acids of all biodiesel sam- the nine biodiesel samples. Two measurements are presented for
ples used in this study. This profile was an indication of the raw each sample, spaced approximately 3 weeks apart. It should be
materials used for the production of methyl esters. B-4 and B-9 mentioned, that certain biodiesel properties such as those of acid
samples were palm-based methyl esters probably blended with a value, water content and ester content were not found to signifi-
significant amount of coconut oil because of the high content of cantly differ during the test period.
lauric acid (C12:0). B-5, B-6 and B-8 samples were soy-based The samples of B-1, B-2, B-3 and B-7 were found well below the
methyl esters probably blended with palm oil and/or used frying minimum induction period of 6 h. These samples mainly com-
oils. prised unsaturated methyl esters and were free of antioxidant
14
of parameters were changed, mainly due to the higher volatility 13
of hydrocarbon fuels compared to methyl esters, which may lead 12
to higher sample evaporation. The changes include elongated reac- 11
tion vessels and higher amount of distilled water, while the evalu- 10
ation of the IP can be only performed manually (2 tangents). All 9
stability measurements were carried out on a Metrohm 873 Bio- 8 EN 14214 Limit
diesel Rancimat Instrument. Samples of 3 g of pure biodiesel and 7
Table 4
Fatty acid composition of the methyl esters.
Fatty acid B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9
C12:0 – – – 22.71 0.17 – 0.26 0.17 23.1
C14:0 0.20 0.24 0.14 6.61 0.18 0.24 – 0.6 5.89
C16:0 12.38 13.48 8.68 6.31 12.55 7.58 5.4 23.88 9.22
C18:0 3.29 3.24 2.52 2.3 2.1 2.7 2.86 3.71 2.47
C18:1 23.87 24.89 34.93 22.1 21.85 46.38 24.75 32.22 24.4
C18:2 37.83 36.1 30.33 18.38 39.6 17.84 48.2 21.26 19.45
2486 G. Karavalakis et al. / Fuel 89 (2010) 2483–2489
additives. Thus, the influence of compound structure of the fatty 3.2. Oxidation stability of diesel–biodiesel blends
esters and the number of the double bonds was of high importance
on the deterioration of these fuels. A strong inverse relationship Fig. 2a and b presents the experimental results obtained with
was observed between the oxidation stability and the content of the use of the biodiesel samples blended with the low sulphur base
unsaturated fatty acids. The oxidation stability decreased with diesel D-1, whereas Fig. 2c and d the stability results of the blends
the increase of the total contents of linoleic and linolenic acids. with D-2. The results revealed that the blends prepared by the B-1
This result is in agreement with previous studies [17,18]. Based had a negative impact on the oxidation stability. The blends of 10%,
on the abovementioned observations, the stability of B-4 and B-9 7% and 5%, respectively, were found below the minimum induction
samples was found well above the specification limit. This proba- period of 20 h. This may be attributed to the low stability of B-1
bly occurred due to the presence of lauric and palmitic acids, which and to the presence of some impurities and degradation products.
were the major saturated acids in the biodiesel mixture. Another It should be reminded that a high proportion of this sample was
factor, which had a stronger effect than the content of unsaturated produced by the transesterification of used frying oils. These oils
acids on the stability of biodiesel, was the presence of antioxidant usually contain short chain organic acids, aldehydes and keto com-
additives. B-5, B-6 and B-8 samples, which comprised of unsatu- pounds, which are products susceptible to further degradation. De-
rated fatty acids, resulted in significantly higher oxidation stability spite the fact that B-2, B-3 and B-7 failed for oxidation stability,
compared to the samples that were known to not contain any their blends with both diesel fuels presented an opposite trend.
additives. This phenomenon may be attributed to several reasons. The most
a 60 b 80
B-1 75 B-6
55
B-2 B-7
70
B-3 B-8
50 B-4 65 B-9
B-5
Induction period, h
45 60
Induction period, h
55
40
50
35 45
40
30
35
25 30
.
25
20
EN 590 Limit
EN 590 Limit
20
15
15
10 10
2 3 4 5 6 7 8 9 10 1 2 3 4 5 6
Biodiesel concentration, %v/v Biodiesel concentration, %v/v
c 90 d 90
.
85 B-1 85 B-6
B-2 B-7
80 80
B-3 B-8
75 75
B-4 B-9
70 B-5 70
Induction period, h
Induction period, h
65 65
60 60
55 55
50 50
45 45
40 40
35 35
30
.
30
.
25 25
EN 590 Limit
20 20
EN 590 Limit 15
15
10 10
2 3 4 5 6 7 8 9 10 1 2 3 4 5 6
Fig. 2. Oxidation stability of the biodiesel blends with the low sulphur base diesels D-1 (a, b) and D-2 (c, d).
G. Karavalakis et al. / Fuel 89 (2010) 2483–2489 2487
Induction time, h
correlation between the biodiesels with antioxidant additives 40
and those without, regarding their behavior in oxidation stability
with the base diesel fuels. The biodiesel samples treated with addi- 35
tives behaved better than those without, when blended with D-1.
This was not the case for B-8 which demonstrated a significantly 30
higher stability compared to the other biodiesel samples but re-
sulted in poor stability performance when blended with diesel fuel. 25
.
On the other hand, the additized biodiesel blends with D-2 resulted EN 590 Limit
in lower oxidation stability compared to the other blends. 20
50
lower stability. Additionally, the stability of the blends may also
be affected by certain characteristics of the diesel fuel. Higher
refining to lower sulphur in the base diesel decreases oxidation
40 stability of the final blend. In the absence of sulphur in the base
diesel, which acts as a natural oxidation inhibitor, the presence
of antioxidant additive in the methyl ester had a strong effect on
30 the stability of the final blends. Diesel fuel containing catalyti-
.
35
Acknowledgements
Reproducibility of EN 15751
32.5
The authors wish to thank Hellenic Petroleum SA for supplying
the test fuels and financially supporting this series of experiments.
30
27.5 References
Testing margins at the supplier
[1] Rashid U, Anwar F. Production of biodiesel through optimized alkaline-
Induction period, h
[19] Karavalakis G, Karonis D, Stournas S. Evaluation of the oxidation stability of Evaluation of the chemical stability of diesel fuels by following the kinetics
diesel/biodiesel blends using the modified Rancimat method. SAE Technical of sediment formation. Fuel 1992;71:437–42.
Paper 2009; 2009-01-1828. [21] Liu Z, Yan F. Study on improving oxidation stability of catalytically-cracked
[20] Kalitchin ZD, Ivanov SK, Tanielyan SK, Boneva MI, Georgiev PT, Ivanov A, et al. diesel oil. Petroleum Sci Technol 2003;21:1887–95.
Chemical stability of diesel fuels and sediment formation therein: 1.