Fuel 88 (2009) 732737

Contents lists available at ScienceDirect

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

Effect of commercially available antioxidants over biodiesel/diesel blends stability

Rosen Dinkov *, Georgi Hristov, Dicho Stratiev, Violeta Boynova Aldayri
LUKOIL Neftochim Bourgas Bulgaria, Research Laboratory, Bulgaria

a r t i c l e

i n f o

a b s t r a c t
The main obstacle in biodiesel/conventional diesel blends acceptance worldwide seems to be its poor oxidative stability. Low resistance towards oxygenation is due to the fatty constituent in the blend. Even low concentrations of biodiesel (5%, 10% and 20%) can contribute to sticky, viscous and polymeric deposits formation after several months of storage. Two correlations were derived concerning insolubles formed in both stabilized and not stabilized blends, stressed under conditions of ASTM D2274. For treated with antioxidant additive:

Article history: Received 22 March 2008 Received in revised form 19 September 2008 Accepted 22 September 2008 Available online 16 October 2008 Keywords: Oxidation stability Antioxidant Biodiesel blends

Total insol: 0:6561 80:1213 DTAN 114:27 DPC 2:6073 DIV

For not stabilized samples:

Total insol: 229:348338 13:2360978 DTAN 968:531862 DVisc: 25:0335999 DIV

The correlations precision is described by the high value of R2 = 1.0000. Present work proves that it is possible to stabilize such a blend even the fatty component is aged for a period of three months. 2008 Elsevier Ltd. All rights reserved.

1. Introduction The Commission Green Paper Towards an European strategy for the security of energy supply, sets the objective of 20% substitution of conventional fuels by alternative fuels in the road transport sector by the year 2020 [1]. Biodiesel is an alternative diesel fuel consisting of alkyl monoesters of fatty acids prepared from vegetable oils. It has been the focus of a considerable amount of recent research because it is renewable, reduces the emission of some pollutants, and is also readily biodegradable in the environment [2,3]. The geographical situation of Bulgaria determines the ability of our agriculture to produce mainly sunower and rapeseed oils. These oils are well known for their good cold weather performance, determined from type of fatty acid distribution [4]. As a new product a detailed analyses of different fatty acid methyl esters (FAME)/diesel blends were conducted in Lukoil Neftochim Bourgas (LNB) research laboratory [5]. The results showed expected increase in viscosity, density, ash point, TAN, water content, iodine value, lubricity and slight increase in cold lter plugging point (CFPP) in comparison with conventional diesel. A decrease was observed in cetane number, sulphur content and polycyclic aromatic hydrocarbons content. Nevertheless the above trends, blends with up to 20% (v/v) FAME fulll the technical requirements of EN590 [18]. The bottle-neck of blends appeared to be its oxidative stability, also pointed in [3,4,6].
* Corresponding author. Tel.: +35 9885498864. E-mail address: dinkov.rosen.k@neftochim.bg (R. Dinkov). 0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2008.09.017

Because of its chemical structure, biodiesel can be very sensitive to oxidative and thermal degradation. The sensitivity varies depending on the feedstock and the presence of naturally occurring antioxidants in the nished fuel. Oxidation can lead to the formation of corrosive acids and deposits that may cause increased wear in engine fuel pumps [7,8]. The instability is a major barrier to increased acceptance of biodiesel by engine and fuel injection equipment manufacturers, and thus to increased markets for this fuel [7]. For over 80 years, antioxidants have either been used or proposed for use to control fatty oil oxidation. However, when used in fatty oils and esters, naturally occurring antioxidants have consistently been shown to be much less effective than synthetic antioxidants [9]. Effective concentrations appear to be usually within the range of 2001000 ppm, depending on the substrate and the type of stability test used to evaluate additive performance. Apparently, the greatly different chemical structure of esters compared to non-polar hydrocarbons has a signicant effect on antioxidant performance of phenolic compounds [10,11]. The aim of this study is both to evaluate antioxidants additive performance and to track the chemical and physical changes that occur during oxidation in blends with higher than 5% biodiesel content. 2. Experimental 2.1. Materials Untreated with additive rapeseed oil methyl ester (RME) originally manufactured by Biodreams (Lovech, Bulgaria) was supplied

R. Dinkov et al. / Fuel 88 (2009) 732737

733

to LNB. The pure biodiesel was aged (stored in a tank) for a period of three months in order to exceed induction period with the purpose of obtaining greater difference in insolubles for treated with antioxidant and untreated biodiesel/diesel blends. Blends with 5%, 10%, 20% and 30% (v/v) RME were prepared. The conventional constituent of the blends was LNB low sulphur diesel fuel produced according [18] to requirements. Table 1 summarizes the chemical and physical properties of biodiesel and petrol diesel. Table 2 presents tested commercial antioxidants their chemical and physical characteristics. 2.2. Methods ASTM D2274 [12] is the only method adopted for evaluation of biodiesel/diesel blends stability in EN590. It was used to determine the oxidation resistance of biodiesel/diesel blends both with and without antioxidants. A 350 ml volume of ltered blend was aged at 95 C (203 F) for 16 h. Oxygen was bubbled through the sample at a rate of 3 L/h. After aging, the sample was cooled to approximately room temperature before ltering to obtain the lterable insolubles quantity. Adherent insolubles were then removed from the oxidation cell and associated glassware with trisolvent (a mixture of equal parts toluene, acetone and methanol). The trisolvent was evaporated to obtain the quantity of adherent insolubles. The sum of the lterable and adherent insolubles, expressed as milligrams per 100 ml, was reported as total insolubles. Whatman GF/ F pair of lters (47 mm diameter) were used one on top of the other. It happens sometimes that the weight of the upper lter is smaller. Thats why lterable insolubles are not always the most correct measurement of biodiesel/diesel blends oxidation resistance. This method was modied especially for use with biodie-

sel/diesel blend. 100 ml of the aged, ltered fuel was mixed with 400 ml of iso-octane to precipitate any polar polymeric materials that may have formed as a result of ageing. The aged fuel/iso-octane mixture was ltered through a separate pair of lters. A result in the formation of insolubles was observed, because the oxidized and polar polymers that were formed were soluble in the biodiesel. Dilution with a non-polar solvent, such as iso-octane, was shown to result in precipitation of these polymers. After ltering the aged sample, but prior to solvent washing of the lters, an aliquot of the ltrate was obtained for additional testing. The aliquot was analyzed for density at 15 C [13]; kinematic viscosity at 40 C [14]; total acid number (TAN) [15]; peroxide content [16]; iodine value [17]. 3. Results and discussion 3.1. Changes occurring in samples at the conditions specied in ASTM D2274 Fatty oil oxidation is a multi-step reaction process where primary products (conjugated diene and hydroperoxides) decompose and chemically interact with each other to form numerous secondary oxidation products (aldehydes, aliphatic alcohols, formic acid, formate esters, shorter chain fatty acids and species with higher molecular weights) [10]. Stressing the four biodiesel/diesel blends under the conditions specied for the test method resulted in changing its chemical and physical properties. Figs. 15 reveal values characterizing the above changes. Data concerning Figs. 15 can be presented graphically with two linear curves (for both before and after oxidation). The steeper one describes blends with biodiesel concentration from 0% to 5%

Table 1 Chemical and physical properties of biodiesel, and petrol diesel No. Properties Unit Value Diesel 1 2 3 4 Density at 15 C Cetane number Cetane index Sulphur content kg/m3 841.1 51.0 49.3 45.5 Biodiesel 886.3 54.0 6.5 EN ISO 3675 EN ISO 5165 EN ISO 4264 EN ISO 20846 EN ISO 20884 EN ISO 14596 + AC EN ISO 2719 EN ISO 10370 EN ISO 6245 EN ISO 2160 EN ISO 3104 EN ISO 12937 EN 12662 EN ISO 12205 ISO 12156-1 EN12916 EN ISO 3405 Test method

mg/kg

5 6 7 8 9 10 11 12 13 14 15

16

Flash point Carbon residue (on 10% distillation residue) Ash content Copper strip corrosion (3 h at 50 C) Viscosity at 40 C Water content Total contamination Oxidation stability Lubricity, corrected wear scar diameter (wsd 1,4) at 60 C Polycyclic aromatic hydrocarbons Distillation range % recovered at 250 C % recovered at 350 C 95% recovered at CFPP

C % (m/m) % (m/m) class mm2/s mg/kg mg/kg g/m3 lm % (m/m) % (v/v) % (v/v) C C

73.5 0.01 0.001 1a 2.60 26 4.0 8 421 5.9 39 98.5 337 18

177 0.008 1a 4.11 310 9.8

EN116

Table 2 Chemical and physical characteristics of used commercial antioxidants Antioxidant additive Active component Compound (A) (B) (C) 2,6-di-tert.-butyl-1,2-dihydroxybenzene Butylated phenol 2,6-di-tert.-butyl-phenol Mono + tri-tert.-butyl-phenol Quantity (%) 3060 7079.9 75 25 Chemical and physical properties Viscosity at 40 C, cSt 21 7 8 Density at 15 C (kg/cm3) 0.915 0.930 0.940 (at 20 C) Flash point (C) >100 88 >100 Pour point (C) 18 51

734

R. Dinkov et al. / Fuel 88 (2009) 732737

0,88

Iodine value, gJ2/100g

Density, g/cm3

0,87 0,86 0,85 0,84 0,83 0

y(5-30) = 0,001x + 0,8474 R2 = 0,9996 y(5-30) = 0,0004x + 0,8387 R2 = 0,9989

14 12 10 8 6 4 2 0 0 5

y(5-30) = 0,2915x + 4,1827 R2 = 0,9716

y(5-30) = 0,2706x + 2,3481 R2 = 0,9874

10

15 BO AO

20

25

30

10

Biodiesel in blend, %

15 20 Biodiesel in blend, % BO AO

25

30

35

Fig. 1. Biodiesel concentration inuence over density before (BO) and after oxidation (AO).

Fig. 5. Biodiesel concentration inuence over iodine value before (BO) and after oxidation (AO).

5 Viscosity, mm2/s 4,5 4 3,5 3 2,5 2 0 5 10 15 20 25 30 Biodiesel in blend, % BO AO y(5-30) = 0,0149x + 2,5576 R2 = 0,998 y(5-30) = 0,0592x + 2,7432 R2 = 0,9878

and the second for concentration between 5% and 30%. Some countries in European Union have already put an obligation limit for biodiesel content in diesel fuel and the world consumption of biodiesel will also increase [18]. That is why the slope of the second linear line is under study in this paper.The change can be explained by the slope of the straight line, describing the dependence of the above mentioned properties from content of biodiesel in the blend. The larger the absolute value of the slope, the steeper the line and the greater is the increase. Parallel straight lines (equal value of slopes) for a property before (BO) and after oxidation (AO the sample is stressed under conditions of ASTM D2274) will mean that this property depends mainly on biodiesel concentration

Fig. 2. Biodiesel concentration inuence over viscosity before (BO) and after oxidation (AO).

Change SlopeAO SlopeBO =SlopeBO 100;

10 TAN, mg KOH/g 8 6 4 2 0 0 5

y(5-30) = 0,25x + 1,18 R2 = 0,9526

y(5-30) = 0,0009x + 0,0246 R2 = 0,9898 10 15 20 25 30 35

Biodiesel in blend, % BO AO

Fig. 3. Biodiesel concentration inuence over TAN before (BO) and after oxidation (AO).

3 Peroxide content, % 2,5 2 1,5 1 0,5 0 0

y(5-30) = 0,0178x + 1,9868 R2 = 0,9488

y(5-30) = 0,0202x + 0,136 R2 = 0,9009

10

15 BO

20 AO

25

30

35

Biodie sel in ble nd, %

Fig. 4. Biodiesel concentration inuence over peroxide content before (BO) and after oxidation (AO).

where Change = increase or decrease of property dependence from biodiesel concentration above 5 vol% in blend (%); SlopeAO = slope of the straight line, characterizing the dependence of a property after passing trough ASTM D2274s conditions from quantity of biodiesel above 5 vol% and SlopeBO = slope of the straight line, characterizing the dependence of a property from quantity of biodiesel above 5 vol%. Peroxide content BO and AO is described by almost parallel straight lines (SlopeBO = 0.0202 and SlopeAO = 0.0178). The decrease of the lines slope is only 13.5%. That means, that there is a denite potential for peroxide development connected rmly with biodiesel percent above 5 vol% in the blend. The same is valid for the iodine number. The decrease only of 7.7% conrms that total olenic unsaturation is inuenced by biodiesel concentration above 5 vol%. An enormous 27,678% increase of TAN straight line slope after oxidation was observed. Development of acidic materials as the samples were oxidized depends not only from the increase of biodiesel concentration above 5 vol% in the blend Fig. 3. The same trend was valid for other test methods connected with the formation of secondary oxidation products but at lower degree respectively 150% increase for densitys slope AO and 297% for viscositys slope AO Figs. 1 and 2. This phenomenon can be explained by the decomposition and inter-reaction between primary oxidation products. Requirement for stable fuel in [19] is connected with the amount of total insolubles formed during heating and passing oxygen through the sample. With delta (D) we described the change in propertys value after the sample is stressed under conditions of ASTM D2274. The value of D (determined from Figs. 15) shows a slight increase in primary oxidation product (DPeroxide content) formation for blend with up to 20% biodiesel. For 30% blend, a decrease was observed. At the same time secondary oxidation products (DTAN and DViscosity) increased for all samples. That means that for 30% biodiesel, decomposition of ROOH was greater than its formation. Table 3 reveals formed insolubles (sum of lterable and

R. Dinkov et al. / Fuel 88 (2009) 732737 Table 3 Deposits quantity of oxidized biodiesel/diesel blends % Biodiesel in blend 5 10 20 30 Insolubles (g/m3) 37.14 237.43 578.29 358.57 Total insolubles (g/m3) 155.14 237.43 578.29 1124.57

735

variables (properties change) with the aim of expressing dependence between them. Changes in density and peroxide content were rejected by this regression.

Insol: 79:50529 204:6308 DTAN 809:261 DVisc: 50:0971 DIV; R 1:000 and standard error 0
P where, Insol. = (lterable insolubles and adherent insolubles), g/ 3 m ; DTAN = TANAOTANBO, mg KOH/g; DVisc. = ViscAOViscBO, mm2/s and DIV = IVAOIVBO, g J2/100 g. The great value of coefcient in front of DVisc. is observed. Viscosity change (polar polymer formation) seems to inuence deposit formation to the greatest extent. In order to evaluate them, blends were diluted with iso-octane. Dilution was shown to result in precipitation of these polymers. Changes in density and peroxide content again were rejected by this regression.
2

adherent deposits) and total insolubles (sum of lterable, adherent and iso-octane insolubles). Figs. 68 describe the dependence between properties change. The linking between TAN and viscosity increase suggests that the formation of polymers is chemically linked to the formation of acidic secondary oxidation products [3]. The statement is proved by equation on Fig. 6 with R2 = 0.9683. Formation of both acidic and polymer products are the main contributors for density increase. A regression from analysis tools in excel (MS ofce) was applied for the dependent variable (insoluble deposits) and independent

Total insol: 229:348338 13:2360978 DTAN 968:531862 DVisc: 25:0335999 DIV; R2 1:000 and standard error 0
P

Viscosity, mm2/s

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 1 2 3

y = 0.3019e0.1895x R2 = 0.9683

where, Total insol. = (lterable insolubles, adherent and iso-octane insolubles), g/m3; DTAN = TANAOTANBO, mg KOH/g; DVisc. = ViscAOViscBO, mm2/s; DIV = IVBOIVAO, g J2/100 g. Adding iso-octane insolubles to the total insolubles resulted in increasing insolubles dependence from viscosity change (Fig. 9). One can conclude that iso-octane insolubles are polar polymeric materials, because their formation resulted in viscosity increase. 3.2. Effect of additive

TAN, mgKOH/g
Fig. 6. Linking between viscosity and TAN increase.

Viscosity, mm2/s

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0.01

y = 0.1734e84.775x R2 = 0.9994

0.015

0.02 Density, g/cm 3

0.025

0.03

Fig. 7. Linking between viscosity and density increase.

For the purpose of this study, additive B was selected (Table 2). It was preferred for its high content of butylated phenol and lower insolubles formation in stabilized with B additive biodiesel/diesel blends in comparison with the other two antioxidants. Two hundred and fty part per million (ppm) from antioxidant B (the most effective among the tree studied additives) was added to the four blends, containing 5%, 10%, 20% and 30% biodiesel. Changes occurring in the ltered and aged samples (as described in ASTM D2274) were compared with ltered and aged samples non-stabilized and described in Section 3.1. Figs. 1014 present differences between aliquots of both stabilized and not stabilized ltrates. The equations describing straight lines are valid for biodiesel concentration in blends from 5% to 30%. Antioxidants inuence over ltrate properties can be explained also with slope of the straight lines, describing the dependence of the above mentioned properties from content of biodiesel in the blend from 5% to 30%. Equal value of slopes means that the antioxidant is alike effective for all studied biodiesel concentrations in

1200

TAN, mgKOH/g

7 6 5 4 3 2 1 0 0.01

Total insolubles, g/m 3

9 8

y = 7.7925Ln(x) + 36.81 R2 = 0.9937

1000 800 600 400 200 0 0.4 0.6

y = 887.05x - 278.92 R2 = 0.9955

0.015

0.02 Density, g/cm3

0.025

0.03

0.8

1 1.2 Viscosity, mm 2/s

1.4

1.6

1.8

Fig. 8. Linking between TAN and density increase.

Fig. 9. Viscosity change inuence over insoluble formation.

736
3 2,5 Peroxide content, % 2 1,5 1 0,5 0 0 5 10 15 20 25 y(5-30) = 0,0178x + 1,9868 R2 = 0,9488

R. Dinkov et al. / Fuel 88 (2009) 732737

10 9 8 TAN,mgKOH/g 7 6 5 4 3 2 1 0 y(5-30) = 0,2791x - 2,1425 R2 = 0,9369 y(5-30) = 0,25x + 1,18 R2 = 0,9526

y(5-30) = 0,1009x - 0,5318 R2 = 0,9348

30

35

10

15

20

25

30

35

Biodie sel in ble nd, % with Antioxidant without Antioxidant

Biodie sel in ble nd, % with Antioxidant without Antioxidant

Fig. 10. Antioxidants effect over peroxide formation.

Fig. 14. Antioxidants effect over TAN.

16 14 Iodine value, gJ2/100g 12 10 8 6 4 2 0 0 5

y(5-30) = 0,2435x + 6,6088 R2 = 0,7887

Table 4 Deposits quantity of oxidized biodiesel/diesel blends treated with 250 ppm of antioxidant B % Biodiesel in blend 5 10 20 30 Insolubles (g/m3) 3.71 0 14.28 287.15 Total insolubles (g/m3) 3.71 0 14.28 301.1

y(5-30) = 0,2706x + 2,3481 R2 = 0,9874

10

15

20

25

30

35

Biodie sel in ble nd, % with Antioxidant without Antioxidant

Fig. 11. Antioxidants effect over total olenic unsaturation.

0,88 0,875 0,87 0,865 0,86 0,855 0,85 0,845 0,84 0,835 0,83 0 5

y(5-30) = 0,001x + 0,8474 R2 = 0,9996

y(5-30) = 0,0013x + 0,8336 R2 = 0,9805

blends. Increase of stabilized samples slope for properties like density (30%), viscosity (15%) and TAN (12%) means that the antioxidant decreased formation of secondary oxidation products with degree slightly depending on biodiesel concentration in the blend. Just the opposite is antioxidants behavior towards primary oxidation products (slope increase = 467%). The higher the percent of biodiesel in the blend, the smallest decrease of hydroperoxides (ROOH) in treated samples with 250 ppm of antioxidant B. Table 4 reveals formed insolubles (sum of lterable and adherent deposits) and total insolubles (sum of lterable, adherent and iso-octane insolubles) occurring in the oxidized, treated with 250 ppm of antioxidant B samples. The same MS ofce regression was applied for the data, obtained from the stabilized samples. Changes in density and viscosity were rejected by this regression.

Density, g/cm3

Insol: 1:136992 76:18682 DTAN 108:436

10 15 20 25 30 35
2

DPC 2:34913 DIV; R 1:000 and standard error 0

Biodiesel in blend, % with Antioxidant without Antioxidant

Fig. 12. Antioxidants effect over density.

P where, Insol. = (lterable insolubles and adherent insolubles), g/ m3; DTAN = TANAOTANBO, mg KOH/g; DPC (Peroxide content) = PCAOPCBO (%); DIV = IVBOIVAO, g J2/100 g.Changes in density and viscosity again were rejected by the regression.

5 4,5 Viscosity, mm2/s 4 3,5 3 2,5 2 0 5 10 15 20 25 30 35 Biodiesel in blend, % with Antioxidant without Antioxidant y(5-30) = 0,0681x + 2,2639 R2 = 0,9845 y(5-30) = 0,0592x + 2,7432 R2 = 0,9878

Totalinsol: 0:6561 80:1213 DTAN 114:27 DPC 2:6073 DIV; R2 1:000 and standard error 0
P

where Total insol. = (lterable insolubles, adherent and iso-octane insolubles), g/m3; DTAN = TANAOTANBO, mg KOH/g; DPC (Peroxide content) = PC AOPCBO (%); DIV = IVBOIVAO, g J2/100 g. Adding iso-octane resulted in increasing total insolubles only for 30% biodiesel in blend.

4. Conclusions Enormous increase in values of properties AO rmly connected with secondary oxidation products (TAN, density and viscosity),

Fig. 13. Antioxidants effect over viscosity.

R. Dinkov et al. / Fuel 88 (2009) 732737

737

shows reaction of decomposition and inter-reaction between primary oxidation products. Formation of both acidic and polymer products are the main contributors for density increase in untreated biodiesel/diesel blends. Soluble in bio-blends materials can be precipitated by dilution with iso-octane. Obtained insolubles are polar polymeric materials, because their formation resulted in viscosity increase. The addition of antioxidant B to biodiesel/diesel blends led to reduction in insolubles formation. This reduction concerns lterable, adherent and iso-octane insolubles. The antioxidant increases blends resistance toward secondary oxidation products formation. Primary oxidation products decrease mostly for stabilized blends with low biodiesel content. For 30% blend ROOH content is equal to that in not stabilized sample with the same concentration of biodiesel. Comparing total insolubles for stabilized (Table 4) and not stabilized (Table 3) samples revealed that antioxidant B was almost equally efcient for 5%, 10% and 20% biodiesels blend. The decrease in deposits was respectively 98% for B5, 100% for B10 and 98% for B20. Furthermore stabilized blends with up to 20% biodiesel satised requirements of EN590 concerning stability (Table 4). For 30% blend, the antioxidant was less effective. It reduced total insolubles with only 73%. References
[1] Directive 2003/30/EC on the promotion of the use of biofuels or other renewable fuels for transport, 8 May 2003.

[2] Zhang Q, Feldman M, Peterson CL. Diesel engine durability when fueled with methyl ester of winter rapeseed oil. American Society of Agricultural Engineers, paper no. 881562. St. Joseph, MI: ASAE; 1988. [3] Bouaid A, Martinez M, Aracil J. Long storage stability of biodiesel from vegetable and used frying oils. Fuel 2007;86. [4] Park JY, Kim DK. Blending effect of biodiesels on oxidation stability and low temperature ow properties. Bioresource Technol 2008;99. [5] Bulletin of Lukoil Neftochim Bourgas, vol. 4; 2006. [6] Knothe G. Some aspects of biodiesel oxidative stability. Fuel Process Technol 2007;88. [7] An evaluation and comparison of test methods to measure the oxidation stability of neat biodiesel, September 2003May 2005. San Antonio, Texas: SR. Westbrook Southwest Research Institute. [8] Terry B, McCormick RL. Natarajan M. Impact of biodiesel blends on fuel system component durability, SAE Techn. Paper No. 2006-01-3279; 2006. [9] Liang Y, May C, Foon C, Ngan M. The effect of natural and synthetic antioxidants on the oxidative stability of palm diesel. Fuel 2006;85. [10] Characterization of biodiesel oxidation and oxidation products, CRC Project No. AVFL-2b, November 2005. [11] Dunn R. Effect of antioxidants on the oxidative stability of methyl soyate (biodiesel). Fuel Process Technol 2005;86. [12] ASTM D2274. Standard test method for oxidation stability of distillate fuel oil (Accelerated method), vol. 331. West Conshohocken, PA: ASTM International; 2005. [13] EN ISO 3675. Crude petroleum and liquid petroleum products Laboratory determination of density-Hydrometer method. [14] EN ISO 3104, Petroleum products, Liquid fuels, Fuel oil, Viscosity, Kinematic viscosity, Dynamic viscosity, Mathematical calculations, Test equipment, Calibration, 1996. [15] ATSM D664. Standard test method for acid number of petroleum products by potentiometric titration, vol. 331. West Conshohocken, PA: ASTM International; 2005. [16] GOST 10003-90 - Styrene. Specications. [17] ASTM D1959. Standard test method for iodine value of drying oils and fatty acids, vol. 331. West Conshohocken, PA: ASTM International; 2006. [18] <http://www.abengoa-bioenergy.com/>. [19] EN590:2004, Automotive fuels, diesel. Requirements and test methods.