Anda di halaman 1dari 7

Fuel 89 (2010) 2483–2489

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Evaluation of the oxidation stability of diesel/biodiesel blends


George Karavalakis *, Stamoulis Stournas, Dimitrios Karonis
Laboratory of Fuels Technology and Lubricants, School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechniou Str.,
Zografou Campus, 15780 Athens, Greece

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.

1. Introduction ters are more vulnerable to oxidation than monounsaturated


esters because they contain more allylic methylene configurations
Biodiesel is an alternative diesel fuel consisting of long-chain [10,11]. An additional aspect that can have an impact on the overall
fatty acid methyl esters (FAME) derived from vegetable oils, used oxidation stability of biodiesel is the conformational cis/trans isom-
frying oils and animal fats. Biodiesel is chemically produced erization. It is important to note that while a trans unsaturation is
through the transesterification reaction of a triglyceride with an more stable than a cis unsaturation, conjugated trans unsaturations
alcohol (methanol or ethanol) in the presence of an alkaline or are more sensitive to oxidation than cis unsaturations [12].
acidic catalyst [1]. Several articles report on the beneficial charac- Oxidation stability is thus a parameter that describes the degra-
teristics of biodiesel. It is non-toxic, free of sulphur and aromatics, dation tendency of biodiesel and is of great importance in the con-
readily biodegradable, safe to handle, enhances lubricity and its text of possible problems with engine parts. The main oxidation
main physicochemical properties are comparable to those of con- products are peroxides and hydroperoxides. During further degra-
ventional middle distillate fuels [2–4]. Despite its many advanta- dation, these products form shorter-chain compounds such as low
ges, biodiesel’s nature makes it more sensitive to oxidation than molecular weight acids, aldehydes, ketones and alcohols [13,14].
petroleum diesel during long-term storage. The sensitivity varies, The presence of alcohols decreases the flash point and the presence
depending on the raw material, the presence of naturally occurring of acids increases the total acidity and the risk of corrosion [15].
antioxidants and the storage conditions [5,6]. Further reactions with the unstable hydroperoxide species with
The biodiesel stability generally depends on the fatty acid pro- another fatty acid chain may form high molecular weight materi-
file of the parent feedstock. Therefore, biodiesels with high con- als, such dimer or trimer acids which may lead to filter blocking,
tents of unsaturated fatty acids, such as linoleic and linolenic, are injector failures and deposit formation [16].
especially prone to oxidation [7]. The relative oxidation rates for Since oxidative stability significantly affects fuel quality, the
these unsaturated esters are linolenic > linoleic  oleic [8]. This European Commission mandated the European Committee for
is attributed to the fact that these unsaturated fatty acid chains Standardization (CEN) to develop standard specifications and test
contain the most reactive sites which are particularly susceptible methods concerning biodiesel oxidation stability. This issue has
to the free-radical attack. Biodiesel stability is mainly related on been addressed in the European FAME standard EN 14214 and in
the number and position of bis-allylic methylene moieties adjacent the recent version of the European standard for automotive diesel
to the double bond and not to the total number of double bonds ex- (EN 590:2009). The latter requires the determination of oxidation
pressed by the iodine value [9]. Thus, polyunsaturated methyl es- stability of diesel/biodiesel blends using the modified Rancimat
method EN 15751. The finished blends of diesel fuel with biodiesel
* Corresponding author. Tel.: +30 2107723213; fax: +30 210 7723163. shall comply with a minimum induction period of 20 h at 110 °C.
E-mail address: gkaraval@mail.ntua.gr (G. Karavalakis). The established European standard EN 14112 using a Rancimat

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.

Property D-1 D-2 D-3 D-4 EN 590 limits Test method


Viscosity (mm2/s, 40 °C) 2.9 3.2 3.3 2.84 2.00–4.50 EN ISO 3104
Density (g/cm3, 15 °C) 0.8439 0.834 0.8325 0.8355 0.820–0.845 EN ISO 3675
Flash point (°C) 65 82 86 69 55 min EN ISO 2719
Sulphur content (lg g 1) 37 44.6 8 4 50 max
10 max EN ISO 20846
(EN 590:2008)
Water content (lg g 1) 46 100 120 52 200 max EN ISO 12937
Cold filter plugging point, CFPP (°C) 5 7 0 20 5 min EN 116
Distillation EN ISO 3405
IBP 163 197 197 164
10 209 238 238 202
50 276 282 279 272
90 337 333 336 342
FBP 375 367 373 363
Polycyclic aromatic hydrocarbons (% m/m) 4.6 4.5 2.7 1.2 11 max EN 12916

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).

Property B-6 B-7 B-8 B-9 EN 14214 limits Test method


2
Viscosity (mm /s, 40 °C) 4.36 4.14 3.34 3.7 3.50–5.00 EN ISO 3104
Density (g/cm3, 15 °C) 0.8813 0.8844 0.8788 0.8767 0.860–0.900 EN ISO 3675
Water content (lg g 1) 305 786 630 470 500 max EN ISO 12937
Cold filter plugging point, CFPP (°C) 4 3 1 1 +5 max EN 116
Iodine number 100 125.8 79 61 120 max EN 14111
Acid value (mgKOH/g) 0.49 0.54 0.47 0.29 0.50 max EN 14104
Oxidation stability (110 °C, h) 9.74 3.81 18.57 8.75 6 h min EN 14112
Monoglyceride content (% m/m) 0.80 0.74 0.41 0.52 0.80 max EN 14105
Diglyceride content (% m/m) 0.12 0.04 0.06 0.19 0.20 max EN 14105
Triglyceride content (% m/m) 0.11 0.08 0.086 0.11 0.20 max EN 14105
Total glycerol (% m/m) 0.240 0.206 0.125 0.106 0.25 max EN 14105
Ester content (% m/m) 97.4 98 98 98.1 96.5 min EN 14103
Linolenic acid methyl ester (% m/m) 4.43 0.29 0.26 0.32 12 max EN 14103

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

2.3. Oxidation stability measurements


20
19 1st Run
The oxidation stability was quantified by the induction period 2nd Run
18
(IP) of neat methyl esters and their blends with automotive diesel.
17
The IP was evaluated according to the Rancimat method EN 14112
16
for pure biodiesel and the modified Rancimat method EN 15751 for 15
the biodiesel blends. In the modified Rancimat method, a number
Induction period, h

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

7.5 g of biodiesel blends respectively, were analyzed under con- 6


5
stant air flow of 10 L/h passing through the fuel and into a vessel
containing distilled water (HPLC water). The samples were held 4
3
at 110 °C heating block temperature, with a temperature correc-
2
tion factor DT to be set to 1.5 °C (as recommended by the test
1
method). As soon as volatile organic acids (mainly acetic and for-
0
mic) are formed in the sample, this is indicated by an increase in
conductivity in the measuring vessel. The time that elapses until B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9
the secondary oxidation products are detected, is known as the
Fig. 1. Changes on the oxidation stability of the methyl esters during storage.
induction period.

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

Biodiesel concentration, %v/v Biodiesel concentration, %v/v

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

probable explanation was that these samples were at different


a 60
stages of their oxidation. B-1 was supplied and stored three
B-3
months prior to the test program, while B-2, B-3 and B-7 were 55 B-5
fresh samples.
B-7
Moreover, some noticeable differences were observed when 50 B-8
comparing the same biodiesel blends with the two base diesel B-9
fuels. B-3, B-5, B-7, B-8 and B-9 biodiesel blends resulted in lower 45
stability performance with D-1 compared to D-2. There is a weak

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

Fig. 3a and b shows the oxidation stability of the biodiesel


15
blends with the ultra low sulphur diesels, D-3 and D-4 respec-
tively. Most biodiesel blends presented lower induction times
10
compared to those obtained with D-1 and D-2. This phenomenon
was mainly attributed to the absence of sulphur and aromatic com- 2 3 4 5 6 7 8 9 10
pounds in the fuels [19]. Sulphur compounds may act as natural Biodiesel concentration, %v/v
oxidation inhibitors in the fuel oil and their presence usually slows
50
down the aging of the fuel and prevents the formation of acids and b B-3
sludge [16,20]. It was also observed that the blends prepared with
B-5
D-3 resulted in higher stability than those prepared with D-4. An- 45
B-7
other interesting observation was that the presence of antioxidant B-8
additives in biodiesel had a stronger effect on the stability of the B-9
40
final blends with the ultra low sulphur diesel than the low sulphur
fuels. It is reasonable to assume that when sulphur was virtually
Induction time, h

absent in the base diesels, the oxidation mechanisms were favor- 35

ably influenced by the presence of antioxidant additives in the


methyl ester samples. This result probably indicates an inverse 30
correlation relationship between sulphur content and antioxidant
additives.
25
Although it is believed that the type of feedstock and the chem-
ical composition of biodiesel may affect the oxidation stability, the
EN 590 Limit
experimental results revealed that these factors were not signifi- 20
cant on the stability of the final blends. The fatty acid composition
of the biodiesel samples displayed small differences, which were
15
not important enough to justify the observed differences in the sta-
bility of the blends. The same observation holds for the acid value
where the differences were marginal and do not warrant great 10
fluctuations in the stability of the finished blends. Thus, the chem- 2 3 4 5 6 7 8 9 10
ical structure and certain properties of biodiesel cannot be consid- Biodiesel concentration, %v/v
ered as the major factors influencing the oxidation stability of the
biodiesel blends. On the contrary, the stability of the blends seems Fig. 3. Oxidation stability of the biodiesel blends with the ultra low sulphur diesels,
to be affected by the stage of oxidation of the methyl ester (fresh or D-3 (a) and D-4 (b).
aged sample), the presence of additives, and the quality of the base
diesel fuel.
3.4. Determination of precision data in accordance to the modified
Rancimat method
3.3. Effects of diesel fuels on the oxidation stability of methyl esters
Fig. 5 shows a typical example of the stability of biodiesel
As abovementioned, the quality and composition of diesel fuel blends as a function of biodiesel concentration. The particular sam-
may significantly affect the oxidation stability of biodiesel blends. ple was prepared by blending B-1 with the base diesel D-2. In order
Fig. 4 shows the stability of the average values of all biodiesel sam- to increase the general acceptance and use of biodiesel, consumer
ples employed in this study. The impact of base fuel type on the confidence in the fuel reliability, quality and performance must be
oxidation stability was clear, with D-2 presenting higher stability high. This cannot be the case if there is a large variation in the
followed by D-1, D-3 and D-4. The higher stability performance properties of biodiesel blends and on the exact concentration of
of D-2 and D-3 compared to D-1 and D-4, respectively, was proba- biodiesel in diesel fuel. For these reasons, an additional analysis
bly due to the absence of cracked stocks in the base diesels since was performed based upon the European Standard EN ISO 4259.
they were hydrotreated straight run atmospheric gasoil of mainly This figure presents the acceptability limits, with respect to the
paraffinic type crude oils. The cracking process produces compo- reproducibility of the test method (EN 15751). It was evident that
nents of lower stability than straight run distillates [21]. blends contained between 5% and 10% biodiesel were below the
2488 G. Karavalakis et al. / Fuel 89 (2010) 2483–2489

80 investigate the oxidation stability of the final blends. It was found


D-1 that the stability of the biodiesel blends is a very complex process
D-2 that is affected by a variety of factors, including the composition of
70
D-3 biodiesel, the presence of antioxidant additives, and its stage of
D-4 oxidation. In general, the stability of the biodiesel component is re-
flected on the stability of its blends with diesel fuel. Moreover, a
60
strong correlation between biodiesel concentration and blend sta-
bility was observed. Increasing biodiesel concentration results in
Induction period, h

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-
.

cally-cracked compounds seemed to be more unstable, compared


EN 590 Limit to hydrotreated straight run diesel fuel.
20
The results of this study revealed that further work is required
to be done in order to fully evaluate the actual mechanisms that
10
may affect to oxidation stability of diesel/biodiesel blends. The
experimental data provided the basis for future work regarding
2 3 4 5 6 7 8 9 10 the detailed investigation on the impact of diesel fuel composition
Biodiesel concentration, %v/v on the stability of the finished blends, a more in depth evaluation
of biodiesel chemical structure on the oxidation stability, and the
Fig. 4. Comparison of the base diesel fuels with the average values of all methyl
ester samples.
effect of various synthetic antioxidant additives on the oxidation
behavior of diesel/biodiesel blends.

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

25 catalyzed transesterification of rapessed oil. Fuel 2008;87:265–73.


[2] Schinas P, Karavalakis G, Davaris C, Anastopoulos G, Karonis D, Zannikos F,
22.5 et al. Pumpkin (Cucurbita pepo L.) seed oil as an alternative feedstock for the
production of biodiesel in Greece. Biomass Bioenergy 2009;33:44–9.
[3] Bautista LF, Vicente G, Rodriguez R, Pacheco M. Optimization of FAME
20 production from waste cooking oil for biodiesel use. Biomass Bioenergy
EN 590 Limit 2009;33:862–72.
[4] Raheman H, Ghadge SV. Performance of compression ignition engine with
17.5
mahua (Madhuca indica) biodiesel. Fuel 2007;86:2568–73.
[5] Dunn RO. Antioxidants for improving storage stability of biodiesel. Biofuels,
15 Bioproducts Biorefining 2008;2:304–18.
[6] Tang H, De Guzman RC, Salley SO, Ng SKY. The oxidative stability of biodiesel:
Testing margins at the recipient effects of FAME composition and antioxidant. Lipid Technol 2008;20:249–52.
12.5 [7] Das LM, Bora DK, Pradhan S, Naik MK, Naik SN. Long-term storage stability of
biodiesel produced from Karanja oil. Fuel 2009;88:2315–8.
10 [8] Knothe G. Some aspects of biodiesel oxidative stability. Fuel Process Technol
2007;88:669–77.
2 6 10
0 4 8 [9] Knothe G. Structure indices in FA chemistry. How relevant is the iodine
number. Am Oil Chem Soc 2002;79:847–54.
Biodiesel concentration, %v/v [10] McCormick RL, Ratcliff M, Moens L, Lawrence L. Several factors affecting the
stability of biodiesel in standard accelerated tests. Fuel Process Technol
Fig. 5. Evaluation of the acceptance limits and the reproducibility of the modified 2007;88:651–7.
Rancimat method in accordance to EN ISO 4259. [11] Ogawa T, Kajiya S, Kosaka S, Tajima I, Yamamoto M, Okada M. Analysis of
oxidative deterioration of biodiesel fuel. SAE Technical Paper 2008; 2008-01-
minimum induction period of 20 h. Specifically, B10 failed even the 2502.
[12] Fang HL, McCormick RL. Spectroscopic study of biodiesel degradation
testing margin at the recipient. On the other hand, only the two pathways. SAE Technical Paper 2006; 2006-01-3300.
lower biodiesel blends (B2 and B3) were clearly above the testing [13] Schober S, Mittelbach M. The impact of antioxidants on biodiesel oxidation
margin at the supplier. It should be noted that, based on the repro- stability. Eur J Lipid Sci Technol 2004;106:382–9.
[14] Tang H, Abunasser N, Wang A, Clark BR, Wadumesthrige K, Zeng S, et al.
ducibility of the test method, the differences between similar bio- Quality survey of biodiesel blends sold at retail stations. Fuel 2008;87:2951–5.
diesel blends regarding their oxidation stability should be [15] Paligova J, Jorikova L, Cvengros J. Study of FAME stability. Energy Fuels
considered as statistically insignificant. 2008;22:1991–6.
[16] Waynick AJ. Characterization of biodiesel oxidation and oxidation products.
CRC Project No. AVFL-2b; 2005.
4. Conclusions [17] Ramos MJ, Fernandez GM, Casa A, Rodriguez L, Perez A. Influence of fatty acid
composition of raw materials on biodiesel properties. Bioresour Technol
2009;100:261–8.
In this study, nine different commercially available methyl es- [18] Knothe G. Analysis of oxidized biodiesel by H-NMR and effect of contact area
ters were blended with four automotive diesel fuels in order to with air. Eur J Lipid Sci Technol 2006;108:493–500.
G. Karavalakis et al. / Fuel 89 (2010) 2483–2489 2489

[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.

Anda mungkin juga menyukai