Abstract

The oxidation stabilizing effect of a substituted phenol on soy and palm based biodiesels was investigated according to the ASTM E2009 standard. Pressure differential scanning calorimetry (PDSC) measurements were used to evaluate the influence of oxygen pressure. A relationship was derived to describe the correlation between oxidation onset temperature and oxygen pressure. Additional standard differential scanning calorimetry (DSC) and thermogravimetric analysis tests were performed in order to evaluate other thermal effects of the additive. The different behavior of both fuels was explained on the basis of their different physical and chemical properties. PDSC results were compared with the values obtained by the Rancimat method and the crystallization temperature observed by standard DSC was compared with the cold filter plugging point obtained according to the EN 116 standard.

References

1.
Canter
,
N.
, “
Examining Biodiesel Oxidation
,”
Tribology & Lubrication Technology
, Vol.
65
,
2009
, pp.
18
19
.
2.
ASTM D3703-07,
2007
, “
Standard Test Method for Hydroperoxide Number of Aviation Turbine Fuels, Gasoline and Diesel Fuels
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
3.
Demirbas
,
A.
, “
Thermal Degradation of Fatty Acids in Biodiesel Production by Supercritical Methanol
,”
Energy Explor. Exploitation
, Vol.
25
,
2007
, pp.
63
70
. https://doi.org/10.1260/014459807781036421
4.
Arisoy
,
K.
, “
Oxidative and Thermal Instability of Biodiesel
,”
Energy Sources Part A: Recovery Util. Environ. Eff.
, Vol.
30
,
2008
, pp.
1516
1522
. https://doi.org/10.1080/15567030601082845
5.
Guzman
,
R.
,
Tang
,
H.
,
Salley
,
S.
, and
Ng
,
K. Y. S.
, “
Synergistic Effects of Antioxidants on the Oxidative Stability of Soybean Oil- and Poultry Fat-Based Biodiesel
,”
J. Am. Oil Chem. Soc.
 0003-021X, Vol.
86
,
2009
, pp.
459
467
. https://doi.org/10.1007/s11746-009-1373-8
6.
Tang
,
H.
,
Wang
,
A.
,
Salley
,
S.
, and
Ng
,
K. Y. S.
, “
The Effect of Natural and Synthetic Antioxidants on the Oxidative Stability of Biodiesel
,”
J. Am. Oil Chem. Soc.
 0003-021X, Vol.
85
,
2008
, pp.
373
382
. https://doi.org/10.1007/s11746-008-1208-z
7.
Domingos
,
A. K.
,
Saad
,
E. B.
,
Vechiatto
,
W. W. D.
,
Wilhelm
,
H. M.
, and
Ramos
,
L. P.
, “
The Influence of BHA, BHT and TBHQ on the Oxidation Stability of Soybean Oil Ethyl Esters (Biodiesel)
,”
J. Braz. Chem. Soc.
 0103-5053, Vol.
18
,
2007
, pp.
416
423
. https://doi.org/10.1590/S0103-50532007000200026
8.
BS EN 14112,
2003
, “
Fat and Oil Derivatives. Fatty Acid Methyl Esters (FAME). Determination of Oxidation Stability (Accelerated Oxidation Test)
,” British Standards Institution, London, UK.
9.
ASTM D6751-08,
2008
, “
Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
10.
Dunn
,
R. O.
, “
Thermal Analysis of Alternative Diesel Fuels from Vegetable Oils
,”
J. Am. Oil Chem. Soc.
 0003-021X, Vol.
76
,
1999
, pp.
109
115
. https://doi.org/10.1007/s11746-999-0056-9
11.
Dunn
,
R. O.
, “
Analysis of Oxidative Stability of Methyl Soyate by Pressurized-Differential Scanning Calorimetry
,”
Trans. ASAE
 0001-2351, Vol.
43
,
2000
, pp.
1203
1208
.
12.
Souza
,
A. G.
,
Danta
,
H. J.
,
Silva
,
M. C. D.
,
Santos
,
I. M. G.
,
Fernandes
,
V. J.
,
Sinfronio
,
F. S. M.
,
Teixeira
,
L. S. G.
, and
Novak
,
C. S.
, “
Thermal and Kinetic Evaluation of Cottonseed Oil Biodiesel
,”
J. Therm Anal. Calorim.
 1418-2874, Vol.
90
,
2007
, pp.
945
949
. https://doi.org/10.1007/s10973-006-8199-5
13.
Chien
,
Y. C.
,
Lu
,
M.
,
Chai
,
M.
, and
Boreo
,
F. J.
, “
Characterization of Biodiesel and Biodiesel Particulate Matter by TG, TG-MS, and FTIR
,”
Energy Fuels
 0887-0624, Vol.
23
,
2009
, pp.
202
206
. https://doi.org/10.1021/ef800388m
14.
Dantas
,
M. B.
,
Conceicao
,
M. M.
,
Fernandes
,
V. J.
,
Santos
,
N. A.
,
Rosenhaim
,
R.
,
Marques
,
A. L. B.
,
Santos
,
I. M. G.
, and
Souza
,
A. G.
, “
Thermal and Kinetic Study of Corn Biodiesel Obtained by the Methanol and Ethanol Routes
,”
J. Therm. Anal. Calorim.
, Vol.
87
,
2007
, pp.
835
839
. https://doi.org/10.1007/s10973-006-7780-2
15.
ASTM E1858-08,
2008
, “
Standard Test Method for Determining Oxidation Induction Time of Hydrocarbons by Differential Scanning Calorimetry
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
16.
ASTM D6186-08,
2008
, “
Standard Test Method for Oxidation Induction Time of Lubricating Oils by Pressure Differential Scanning Calorimetry (PDSC)
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
17.
ASTM E2009-08,
2008
, “
Standard Test Method for Oxidation Onset Temperature of Hydrocarbons by Differential Scanning Calorimetry
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
18.
Moser
,
B. R.
,
Haas
,
M. J.
,
Winkler
,
J. K.
,
Jackson
,
M. A.
,
Erhan
,
S. Z.
, and
List
,
G. R.
, “
Evaluation of Partially Hydrogenated Methyl Esters of Soybean Oil as Biodiesel
,”
Eur. J. Lipid Sci. Technol.
, Vol.
109
,
2007
, pp.
17
24
. https://doi.org/10.1002/ejlt.200600215
19.
Dunn
,
R. O.
, “
Oxidative Stability of Biodiesel by Dynamic Mode Pressurized-Differential Scanning Calorimetry (P-DSC)
,”
Trans. ASABE
 0001-2351, Vol.
49
,
2006
, pp.
1633
1641
.
20.
Xu
,
Y. X.
,
Hanna
,
M. A.
, and
Josiah
,
S. J.
, “
Hybrid Hazelnut Oil Characteristics and its Potential Oleochemical Application
,”
Ind. Crops Prod.
, Vol.
26
,
2007
, pp.
69
76
. https://doi.org/10.1016/j.indcrop.2007.01.009
21.
Knothe
,
G.
, “
Some Aspects of Biodiesel Oxidative Stability
,”
Fuel Process. Technol.
 0378-3820, Vol.
88
,
2007
, pp.
669
677
. https://doi.org/10.1016/j.fuproc.2007.01.005
22.
Polavka
,
J.
,
Paligová
,
J.
,
Cvengros
,
J.
, and
Simon
,
P.
, “
Oxidation Stability of Methyl Esters Studied by Differential Thermal Analysis and Rancimat
,”
J. Am. Oil Chem. Soc.
 0003-021X, Vol.
82
,
2005
, pp.
519
524
. https://doi.org/10.1007/s11746-005-1103-4
23.
Riesen
,
R.
and
Schawe
,
E. K.
, “
Description of the O2 Pressure Influence on the Oxidation Time of Motor Oils
,”
J. Therm. Anal. Calorim.
, Vol.
83
,
2006
, pp.
157
161
. https://doi.org/10.1007/s10973-005-7053-5
24.
Černý
,
J.
and
Zelinka
,
M.
, “
Oxidation Stability of Lubricants Measured by a PDSC Technique
,”
Pet. Coal
, Vol.
46
,
2004
, pp.
56
62
.
25.
BS EN 116,
1998
, “
Diesel and Domestic Heating Fuels, Determination of Cold Filter Plugging Point
,” British Standards Institution, London, UK.
26.
ASTM D2500-05,
2005
, “
Standard Test Method for Cloud Point of Petroleum Products
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
27.
ASTM D4419-90,
2005
, “
Standard Test Method for Measurement of Transition Temperatures of Petroleum Waxes by Differential Scanning Calorimetry (DSC)
,” Annual Book of ASTM Standards, ASTM International, West Conshohocken, PA.
28.
EN ISO 12937,
2001
, “
Methods of Test for Petroleum and its Products, BS 2000-438, Petroleum Products, Determination of Content
,” Coulometric Karl Fischer titration method, International Organization for Standardization, Geneva, Switzerland.
29.
EN 14104,
2003
, “
Fat and Oil Derivatives, Fatty Acid Methyl Esters (FAME), Determination of Acid Value
,” European Committee for Standardization, Brussels, Belgium.
30.
EN 14103,
2003
, “
Fat and Oil Derivatives, Fatty Acid Methyl Esters (FAME), Determination of Ester and Linolenic Acid Methyl Ester Contents
,” European Committee for Standardization, Brussels, Belgium.
31.
EN 14111,
2003
, “
Fat and Oil Derivatives—Fatty Acid Methyl Esters (FAME) - Determination of Iodine Value
,” European Committee for Standardization, Brussels, Belgium.
32.
EN 14105,
2003
, “
Fat and Oil Derivatives, Fatty Acid Methyl Esters (FAME), Determination of Free and Total Glycerol and Mono-, Di-, Triglyceride Contents (Reference method)
,” European Committee for Standardization, Brussels, Belgium.
33.
EN 14106,
2003
, “
Fat and Oil Derivatives, Fatty Acid Methyl Esters (FAME), Determination of Free Glycerol Content
,” European Committee for Standardization, Brussels, Belgium.
34.
EN 14110,
2003
, “
Vegetable Fats, Vegetable Oils, Animal Fats, Animal Oils, Fatty Scids, Esters (Carboxylic), Determination of Content, Methyl Alcohol, Chemical Analysis and Testing, Fuel Oil, Diesel Fuels, Domestic Fuel Oil
,” European Committee for Standardization, Brussels, Belgium.
35.
ISO 3987,
1994
, “
Petroleum products, Lubricating Oils and Additives, Determination of Sulfated Ash
,” International Organization for Standardization, Geneva, Switzerland.
36.
ISO 3575,
2005
, “
Continuous Hot-Dip Zinc-Coated Carbon Steel Sheet of Commercial and Drawing Qualities
,” International Organization for Standardization, Geneva, Switzerland.
37.
EN ISO 12185,
1996
, “
Crude Petroleum and Petroleum Products—Determination of Density—Oscillating U-tube Method
,” International Organization for Standardization, Geneva, Switzerland.
38.
EN ISO 3104,
1994
, “
Petroleum Products, Transparent and Opaque Liquids, Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity
,” International Organization for Standardization, Geneva, Switzerland.
39.
EN 14538,
2006
, “
Fat and Oil Derivatives, Fatty Acid Methyl Ester (FAME), Determination of Ca, K, Mg and Na Content by Optical Emission Spectral Analysis with Inductively Coupled Plasma (ICP OES)
,” European Committee for Standardization, Brussels, Belgium.
40.
EN 14107,
2003
, “
Fat and Oil Derivatives, Fatty Acid Methyl Esters (FAME), Determination of Phosphorous Content by Inductively Coupled Plasma (ICP) Emission Spectrometry
,” European Committee for Standardization, Brussels, Belgium.
41.
Ushikusa
,
T.
,
Maruyama
,
T.
,
Niiya
,
I.
, and
Masakazu
,
O.
, “
Pyrolysis Behaviour and Thermostability of Polyglycerols and Polyglycerol Fatty Acid Esters
,”
J. Jpn. Oil Chem. Soc.
, Vol.
39
,
1990
, pp.
314
320
.
42.
Fukuda
,
Y.
,
Shibata
,
Y.
, and
Kumazaki
,
T.
, “
Oxidative Stability of Edible Oils (Seeds’ and Nuts’ Oils) by TG and Sensory Evaluation of Nuts Oils
,”
J. Nagoya Womens Univ. Home Econ.Nat. Sci.
, Vol.
49
,
2003
, pp.
117
123
.
43.
2009
AOCS
, Introduction to the Processing of Edible Fats and Oils Module IV: Modification, http://www.aocs.org/meetings/education/mod4sample.pdf (Last accessed on 4 May 2009).
44.
Litwinienko
,
G.
,
Daniluk
,
A.
, and
Kasprzycka-Guttman
,
T.
, “
Study on Autoxidation Kinetics of Fats by Differential Scanning Calorimetry. 1. Saturated C12-C18 Fatty Acids and Their Esters
,”
Ind. Eng. Chem. Res.
 0888-5885, Vol.
39
,
2000
, pp.
7
12
. https://doi.org/10.1021/ie9905512
45.
Litwinienko
,
G.
and
Kasprzycka-Guttman
,
T.
, “
Study on the Autoxidation Kinetics of Fat Components by Differential Scanning Calorimetry. 2. Unsaturated Fatty Acids and Their Esters
,”
Ind. Eng. Chem. Res.
 0888-5885, Vol.
39
,
2000
, pp.
13
17
. https://doi.org/10.1021/ie990552u
46.
Box
,
G. E.
,
Hunter
,
J. S.
, and
Hunter
,
W. G.
,
Estadística para investigadores: diseño, innovación y descubrimiento, 2a Edicción
,
Ed. Reverté
,
Barcelona, Spain
,
2008
, pp.
133
273
.
47.
Tarrío-Saavedra
,
J.
,
López-Beceiro
,
J.
,
Naya
,
S.
, and
Artiaga
,
R.
, “
Effect of Silica Content on Thermal Stability of Fumed Silica/Epoxy Composites
,”
Polym. Degrad. Stab.
 0141-3910, Vol.
93
,
2008
, pp.
2133
2137
. https://doi.org/10.1016/j.polymdegradstab.2008.08.006
48.
van Aardt
,
M.
,
Duncan
,
S. E.
,
Long
,
T. E.
,
O’Keefe
,
S. F.
,
Marcy
,
J. E.
, and
Sims
,
S. R.
, “
Effect of Antioxidants on Oxidative Stability of Edible Fats and Oils: Thermogravimetric Analysis
,”
J. Agric. Food Chem.
 0021-8561, Vol.
52
,
2004
, pp.
587
591
. https://doi.org/10.1021/jf030304f
49.
Zaliha
,
O.
,
Chong
,
C. L.
,
Cheow
,
C. S.
,
Norizzah
,
A. R.
, and
Kellens
,
M. J.
, “
Crystallization Properties of Palm Oil by Dry Fractionation
,”
Food Chem.
, Vol.
86
,
2004
, pp.
245
250
. https://doi.org/10.1016/j.foodchem.2003.09.032
50.
Lopes
,
J. C. A.
,
Boros
,
L.
,
Krähenbühl
,
M. A.
,
Meirelles
,
A. J. A.
,
Daridon
,
J. L.
,
Pauly
,
J.
,
Marrucho
,
I. M.
, and
Coutinho
,
J. A. P.
, “
Prediction of Cloud Points of Biodiesel
,”
Energy Fuels
 0887-0624, Vol.
22
,
2008
, pp.
747
752
. https://doi.org/10.1021/ef700436d
This content is only available via PDF.
You do not currently have access to this content.