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Basic properties of palm oil biodieseldiesel blends


Pedro Benjumea a,*, John Agudelo b, Andres Agudelo b
a

Alternative Fuels Group, Energy Institute, Faculty of Mines, Universidad Nacional de Colombia Sede Medelln, Colombia b Group of Energy Ecient Management GIMEL, Engineering Faculty, Universidad de Antioquia, Colombia Received 16 May 2007; received in revised form 24 October 2007; accepted 12 November 2007 Available online 21 December 2007

Abstract The basic properties of several palm oil biodieseldiesel fuel blends were measured according to the corresponding ASTM standards. In order to predict these properties, mixing rules are evaluated as a function of the volume fraction of biodiesel in the blend. Kays mixing rule is used for predicting density, heating value, three dierent points of the distillation curve (T10, T50 and T90), cloud point and calculated cetane index, while an Arrhenius mixing rule is used for viscosity. The absolute average deviations (AAD) obtained were low, demonstrating the suitability of the used mixing rules. It was found that the calculated cetane index of palm oil biodiesel obtained using ASTM D4737 is in better agreement with the reported cetane number than the one corresponding to the ASTM D976. This result is most likely due to the fact that the former standard takes into account the particular characteristics of the distillation curve. 2007 Elsevier Ltd. All rights reserved.
Keywords: Palm oil biodiesel; Blends; Basic properties; Mixing rules

1. Introduction Biodiesel is currently the most widely accepted alternative fuel for diesel engines due to its technical, environmental and strategic advantages. It has enhanced biodegradability, reduced toxicity and improved lubricity in comparison with conventional diesel fuels. In addition, this biofuel is completely miscible with petroleum diesel, allowing the blending of these two fuels in any proportion. Biodiesel can be used neat or blended in existing diesel engines without signicant modications to the engine. However, dierences in the chemical nature of biodiesel (mixture of mono-alkyl ester of saturated and unsaturated long chain fatty acids) and conventional diesel fuel (mixture of paranic, naphthenic and aromatic hydrocarbons) result in dierences in their basic properties, aecting engine performance and pollutant emissions. Biodiesel, produced from any vegetable oil or animal fat, generally has higher density, viscosity, cloud point and cetane num-

Corresponding author. Tel.: +574 425 5319; fax: +574 234 1004. E-mail address: pbenjume@unalmed.edu.co (P. Benjumea).

ber, and lower volatility and heating value compared to commercial grades of diesel fuel [19]. It is important to know the basic properties of biodiesel diesel blends. Some of these properties are required as input data for predictive and diagnostic engine combustion models. Additionally, it is necessary to know if the fuel resulting from the blending process meets the standard specications for diesel fuels. Given the diculty of obtaining the basic properties of the blend by measurement, the ability to calculate these properties using blending or mixing rules is very useful. Such an approach allows an a priori estimation of blend properties as a function of composition and pure component values. Clements [10] proposed blending rules for estimating the density, heating value, viscosity, cetane number and cloud point of biodiesel as a function of its methyl esters prole. By comparing predicted values with experimental data, he found that the typical average errors were less than 2%, with the exception of viscosity, where the average error was 10%. Similar blending rules to those proposed by Clements for calculating properties of methyl ester blends have also been used by other researchers for estimating properties of biodieseldiesel blends.

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.11.004

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Tat and Van Gerpen [11] presented experimental data for kinematic viscosity of a commercial soybean oil biodiesel and its blends with grade No. 1 and No. 2 diesel fuels at 75%, 50% and 20% biodiesel (by weight), from a temperature close to the biodiesel melting point up to 100 C. Results showed that viscosity increased with the increase in the percentage of biodiesel. The temperature-dependent viscosity behaviour of the blends was similar to that of neat fuels. Blend viscosities were estimated by means of a blending rule, similar to the one proposed by Arrhenius and described by Grunberg and Nissan [12]. The maximum differences between predicted and measured viscosities were less than 2.05% and 3.74% of the measured values for the biodiesel blends with No. 2 and No. 1 diesel fuels, respectively. Tat and Van Gerpen [13] carried out a study on the density of blends similar to that referenced for viscosity [11]. The results indicated a linear type specic gravitytemperature relationship for the soybean oil biodieseldiesel blends that was similar to that of the pure diesel fuels. A mass weighted average was used to estimate blend specic gravities. This simple approach is known in the hydrocarbon industry as Kays mixing rule [14]. Yuan, Hansen and Zhang [15] carried out a study with density similar to that of Tat and Van Gerpen [13], using three types of biodiesel (two produced from soybean oil and another more saturated biodiesel prepared from yellow grease). These were blended with grade No. 2 diesel fuel at 75%, 50% and 25% biodiesel (by weight), and tested from close to the biodiesel crystallization onset temperature up to 100 C. The measurements indicated that all biodiesel fuels and their blends with No. 2 diesel fuel had a linear specic gravitytemperature relationship similar to pure diesel fuel. The densities of the blends estimated by Kays mixing rule showed an average absolute deviation (AAD) of less than 0.43% for all tested fuels in the temperature range studied. Joshi and Pegg [16] presented experimental data for dynamic viscosity and cloud and pour points of biodiesel derived from ethyl esters of sh oil and its blends with No. 2 diesel fuel at 80%, 60%, 40% and 20% biodiesel (by volume). The measurements of the cold ow properties of the blends were correlated as functions of biodiesel content using empirical second-order polynomials, giving regression coecients of 0.996 and 0.995 for the predicted cloud and pour points, respectively. The present paper presents experimental density and viscosity data as a function of temperature, together with the heating value, distillation curves and cloud point for palm oil biodiesel and its blends with No. 2 diesel fuel. Additionally, the calculated cetane index of the tested neat fuels and their blends is obtained by empirical correlations recommended for hydrocarbon fuels. The aim of this work is to evaluate mixing rules for calculating the basic properties of palm oil biodieseldiesel fuel blends as a function of biodiesel content (volume fraction). This approach is more likely to be applicable to other biodiesel fuels and blends

than empirical correlations, which would be valid only for the specic blends tested. 2. Methods 2.1. Blend preparation The biodiesel used in this work was produced in a pilot plant by basic methanolysis of crude palm oil using a methanol/oil molar ratio of 12:1, with 0.6% sodium hydroxide by weight as the catalyst. The reaction temperature and time were 60 C and 1 h, respectively. The methyl ester composition of palm oil biodiesel (POB) was determined by gas chromatography (see Table 1). The commercial grade No. 2 diesel fuel (D) used had an elemental composition by weight of 87.2% carbon, 12.8% hydrogen and 0.0225% sulphur, and an aromatic content of 29.3% (13% monoaromatics, 13.3% diaromatics and 3% polyaromatics). Although several blends with a wide composition spectrum were prepared by splash blending [17], most of the tests were carried out with B5 (5% POB-95% D by volume) and B20 blends, due to their widespread use. Neat fuels are designated as B100 and B0, respectively. Blends were prepared on a volume basis at 25 C. Although blend preparation on a weight basis has the advantage that weight fraction does not change with temperature, the common practice in the fuel industry is to carry out the mixing process on a volume basis at the ambient temperature of the blending location, usually a wholesale commercial plant. For this reason, the option selected in this work was to use blending rules as a function of volumetric fractions. 2.2. Experimental Cloud point was measured according to ASTM D2500 [18]. Density was determined following ASTM 287 [19] using calibrated glass API gravity hydrometers. A mineral oil bath with a temperature control precision of 0.02 C was used for measuring density at dierent temperatures, from close to the cloud point of POB up to 100 C. Kinematic viscosity was determined according to ASTM D445 [20] using a capillary tube viscometer. The calibration constant of the viscometer supplied by the manufacturer is given only for temperatures of 40 and 100 C, so the constant for all other temperatures was linearly interpolated or extrapolated from these values. Both density and kineTable 1 Chemical composition of palm oil biodiesel by GC Fatty acid methyl ester C12:0 C14:0 C16:0 C18:0 C18:1 C18:2 Mass percent 0.267 1.434 46.130 3.684 37.470 11.020

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matic viscosity were measured from the cloud point of POB up to 100 C. High, or gross heating value was determined using an IKA automated bomb calorimeter, following ASTM D240 [21]. All fuels tested were distilled following the procedure established by ASTM D86 [22]. In addition to the initial and nal boiling points, temperatures for distilled percentage multiples of 10 were also registered. The temperature values measured were normalized to standard atmospheric pressure by means of the SidneyYoung correlation, as recommended by ASTM D86. The calculated cetane index for the fuels tested was determined as a function of their densities and distillation curve data using the empirical correlations recommended by ASTM D976 [23] and D4737 [24]. 3. Results and discussion 3.1. Basic properties of pure fuels Experimental data on the basic properties of palm oil biodiesel and diesel fuel are presented in Table 2. The most critical property of POB is its high cloud point, due to its high content of long chain, highly saturated methyl esters (see Table 1). At 16 C POB starts to form crystals. At around 12 C, these crystals may plug lters and fuel lines. These faulty cold ow properties of POB limit its utilization as a neat fuel or in rich biodiesel blends in cold climates or in the winter season. POB is denser, slightly more viscous, and has a narrower boiling interval than diesel fuel, indicating that the fatty acid methyl esters in biodiesel have similar boiling points. Diesel fuel, meanwhile, is composed of a wide variety of hydrocarbons with dierent volatilities. This explains why biodiesel is denser than diesel fuel despite having a lower nal boiling point. POB has a gross heating value lower than diesel fuel due to the presence of oxygen in the methyl ester molecules. This dierence in heating values, expressed as energy per unit mass, is slightly reduced when it is reported as energy per unit volume, given the greater density of POB. As a result of these dierences, the calculated cetane index for POB is higher than for diesel fuel; this agrees with the tendency
Table 2 Basic properties of No. 2 diesel fuel and palm oil biodiesel Properties Density at 25 C Mass high heating value Volume high heating value (25 C) Cloud point Cold lter plugging point Kinematic viscosity at 40 C Initial boiling point Temperature at 50% recovered Final boiling point Calculated cetane index Units
3

reported by several researchers for both cetane numbers and CCI [1,8,9]. 3.2. Eect of temperature In order to analyze the eect of temperature on density and kinematic viscosity of the pure fuels and their blends, the experimental data were tted by means of statistical regressions. Fig. 1 shows the eect of temperature on density (q) for pure fuels and B5 and B20 blends. In the temperature range studied there were no qualitative dierences in the behavior of the fuels tested. Experimental data were correlated by linear regressions, presented in Table 3. The regression coecients (R2) were always greater than 0.99, indicating, as expected, that linear regression accurately represents the densitytemperature relationship for the fuels tested. Viscositytemperature curves for pure fuels and several blends are shown in Fig. 2. As can be seen in this gure, the curves for diesel fuel and for the blends exhibit a similar trend for temperature variation, and these curves are practically identical due to the small dierences in the viscosities of the pure fuels. The variation of kinematic viscosity (g) with temperature for dierent types of uids has been commonly represented by means of Andrade type equations, such as the following [11,25]: g eAB=T C=T
2

The constants (A, B, C) and the regression coecients (R2) for each regression curve shown in Fig. 2 are presented in Table 4.

ASTM Diesel Palm oil standard fuel No. 2 Biodiesel 853.97 45.273 38662 5.0 6.0 4.33 181.5 284.9 384.3 46.3 47.5 864.42 39.837 34436 16.0 12.0 4.71 302.2 326.5 348.9 57.3 50.0

Fig. 1. Variation of blend density with temperature.

kg/m D1298 MJ/kg D240 MJ/m3 D240 C C mm2/s C C C D2500 D6371 D445 D86 D86 D86 D4737 D976

Table 3 Linear regressions parameters for fuel densities Fuel type Linear regression q a bT a B100 B20 B5 B0 882.6689646 876.6406154 873.0569269 869.6231871 b 0.7342772415 0.7115968933 0.6920565595 0.6792453596 R2 0.996686 0.997702 0.994305 0.997307

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these modications, Eq. (3) for a binary mixture takes the form of a geometric volume average (Arrhenius-type equation): ln gB V POB ln gPOB V D ln gD 4

In the above equation, V is the volume fraction and the subscripts are B for blend, POB for biodiesel and D for diesel fuel. For the remaining properties, Kays mixing rule is used: uB
Fig. 2. Variation of blend Kinematic viscosity with temperature.
n X i

xi ui

3.3. Eect of biodiesel content Mixing rules are used for estimating the basic properties of blends as a function of pure fuel properties and biodiesel content. The suitability of these rules is evaluated by means of the absolute average deviation (AAD), calculated as NP 100 X uEXP uPR AAD 2 NP i1 uEXP where NP is the number of experimental points, u is the property to be predicted and the subscripts are EXP for experimental and PR for predicted. The GrunbergNissan mixing rule is widely used for predicting viscosity of liquid mixtures [26]: ln lB
n X i

where uB is the property of the blend and ui is the respective property of the ith component. Using volume fraction instead of molar fraction, Eq. (5) for a binary mixture takes the form of an arithmetic volume average: uB V POB uPOB V D uD 6

3.3.1. Viscosity Fig. 3 shows the eect of biodiesel content on the viscosity of the blends tested for three representative temperatures. As can be seen in this gure, viscosity slightly increases with biodiesel content. The AADs obtained using the selected mixing rule for estimating blend viscosity were 1.07%, 0.64% and 0.72% for the data corresponding to 16, 40 and 100 C, respectively. 3.3.2. Density The variation in blend density with biodiesel content is shown in Fig. 4. As was expected, density is directly proportional to biodiesel content. The AADs obtained using Kays mixing rule to estimate blend densities were 0.13%, 0.15% and 0.09% for the data corresponding to 16, 40 and 100 C, respectively. 3.3.3. Heating value Low heating values (LHV) were calculated from the measured high heating values (HHV), taking into account the elemental composition of the pure fuels and the enthalpy of vaporization of water. As can be seen in Fig. 5, the LHV of blends decreases in direct proportion

xi ln li

n n XX i j

xi xj Gij

where lB is the mean absolute viscosity of the blend, li the absolute viscosity of pure ith component, xi and xj the mole fractions of the ith and jth components, Gij the interaction parameter (Gij = 0, for i = j), and n the number of components. When the components of a mixture have similar chemical structure it is expected that they do not interact with each other and consequently the interaction parameter in Eq. (3) can be neglected. Biodieseldiesel fuel blends can be assumed to behave this way because both liquids are non-polar, completely miscible, and when blended their volumes are practically additive. In this work the volume fraction and the kinematic viscosity are used instead of the mole fraction and absolute viscosity, respectively. With
Table 4 Regression parameters for viscosity Fuel type Regression equation g eAB=T C=T A B100 B30 B20 B5 B0 0.364206158 0.192149860 0.162400318 0.220089863 0.142954422 B 55.22818898 60.09025836 61.85122113 56.0562369 60.16294716 C 416.2888996 462.560271 491.0603185 409.7122203 456.709883
2

R2 0.988622 0.989173 0.962320 0.978609 0.98695

Fig. 3. Variation of blend kinematic viscosity with biodiesel content.

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Fig. 4. Variation of blend density with biodiesel content.

curves tend to intercept at a point which denes two zones with dierent behaviour. Before the interception point (approximately 80% distilled percentage), distillation temperature increases with distilled percentage, while after this point the trend is reversed. Fig. 8 shows the eect of biodiesel content on the distillation temperatures corresponding to three representative distilled percentages: 10%, 50% and 90%. These temperatures are designated as T10, T50 and T90, and the maximum values for these are commonly specied in engine fuel quality standards. The ADDs obtained using Kays mixing rule to estimate T10, T50 and T90 for the blends were 2.5%, 1.3% and 1.0%, respectively. 3.3.6. Calculated cetane index The cetane number is a basic property of diesel fuels that indicates ignition characteristics. This parameter can be measured in a specially designed test engine (ASTM D613) or in a constant volume combustion apparatus (ASTM D6890) [5,9]. However, these tests are awkward and expensive. For this reason there have been many attempts to develop methods to estimate the cetane number of a fuel. In order to dierentiate predicted from measured values, the former is called calculated cetane index (CCI), and the latter cetane number [27]. The CCI can be determined using empirical correlations in accordance with the ASTM D976 and D4737. Using ASTM D976, this parameter is obtained as a function of fuel density at 15 C and the T50 distillation curve point. ASTM D4737 additionally

to the biodiesel content. The AAD obtained using Kays mixing rule to estimate the LHV of blends was 0.19%. 3.3.4. Cloud point Fig. 6 shows the eect of biodiesel content on the cloud point (TCP) of the pure fuels and on a wide spectrum of blends. Although the mixing rule allowed an excellent match of the experimental points (see Fig. 6), the AAD obtained was quite high (15.2%). This happened due to the temperature scale used. Changing degrees Celsius to Kelvin gives an AAD of 0.19%. 3.3.5. Distillation curve points Fig. 7 shows the distillation curves for pure fuels and for B5, B20 and B30 blends. As can be seen in this gure, all

Fig. 5. Variation of low heating value with biodiesel content.

Fig. 7. Distillation curves of POB-D blends.

Fig. 6. Variation of cloud point with biodiesel content.

Fig. 8. Variation of distillation curve points wit biodiesel content.

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Table 5 Calculated cetane indexes for pure fuels and B5 and B20 blends ASTM standard Calculated cetane index D D976 D4737 47.8 46.6 B5 48.7 46.9 B20 48.9 47.0 B100 50.3 57.7

are suitable for predicting the basic properties of palm oil biodieseldiesel blends as a function of biodiesel content. The variation of distillation temperature with distilled percentage for the tested blends is not uniform throughout the boiling interval: there is an interception point (approximately 80% distilled percentage) dividing two zones with opposite behaviour. The ASTM D4737 produces a calculated cetane index of palm oil biodiesel in better agreement with the reported cetane number than the corresponding to the ASTM D976. This result is most likely due to the fact that the former standard takes into account the particular characteristics of the distillation curve. Acknowledgements The authors wish to acknowledge the nancial support of COLCIENCIAS (Instituto Colombiano para el Desarr ollo de la Ciencia y la Tecnologa Francisco Jose de Caldas) to the research project 1118-06-17327. They also acknowledge the collaboration of ICP (Instituto Colombi ano del Petroleo). References
[1] Grabosky M, McCormick R. Combustion of fat and vegetable oils derived fuels in diesel engines. Prog Energy Combust Sci 1998;24:12564. [2] Schumacher LG, Wetherell W, Fisher JA. Cold ow properties of biodiesel and its blends with diesel fuel. Presented at the 1999 Annual ASAE meeting, July 21, Toronto, Canada; 1999, Paper: 99-6133. [3] Srivastava A, Prasad R. Triglycerides-based diesel fuel. Renew Sustain Energy Rev 2000;4:11133. [4] Altin R, Cetinkaya S, Yucesu HS. The potential of using vegetable oil fuels as fuel for diesel engines. Energy Convers Manage 2001;42:52938. [5] Knothe G, Matheaus AC, Ryan III TW. Cetane numbers of branched and straight-chain fatty esters determined in an ignition quality tester. Fuel 2003;82:9715. [6] Carraretto C, Macor A, Mirandola S, Stoppato A, Tonon S. Biodiesel as alternative fuel: experimental analysis and energetic evaluations. Energy 2004;29:2195211. [7] Dmytryshyn SL, Dalai AK, Chaudhari ST, Mishra HK, Reaney MJ. Synthesis and characterization of vegetable oil derived esters evaluation for their diesel additive properties. Biores Technol 2004;92: 5564. [8] Knothe G, Van Gerpen J, Krahl J. The biodiesel handbook. Champaign Illinois: AOCS Press; 2005. [9] Knothe G. Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters. Fuel Process Technol 2005;86:105970. [10] Clements DL. Blending rules for formulating biodiesel fuel. Liquid fuels and industrial products for renewable resources. In: Proceedings of the third liquid fuels conference American society of agricultural engineers. Nashville TN. Sept. 1517, 1996; p. 4453. [11] Tat ME, Van Gerpen JH. The kinematic viscosity of biodiesel and its blends with diesel fuel. JAOCS 1999;76(12):15113. [12] Grunberg L, Nissan AH. Mixture law for viscosity. Nature 1949;164:799800. [13] Tat ME, Van Gerpen JH. The specic gravity of biodiesel and its blends with diesel fuel. JAOCS 2000;77(2):1159. [14] Ahmed T. Hydrocarbon phase behaviour. Houston, TX. Gulf Publishing Company; 1989.

Fig. 9. Variation of calculated cetane index with biodiesel content.

takes into account T10 and T90 values. Table 5 shows the CCI values using the two standards. Distillation curve points were taken according to the measured values shown in Fig. 7 and the values of density at 15 C were obtained according to the linear regressions presented in Table 3. For the blends tested (B5 and B20) the eect of biodiesel content on the CCI of the blend was not signicant, and the values obtained using both methods were similar. For B100, the value of the CCI obtained using the ASTM D4737 (CCI4737) was higher than that obtained using the ASTM D976, and was in better agreement with the measured cetane number reported for POB by Malaysian Palm Oil Board researchers [28]. The better prediction obtained using ASTM D4737 is most likely due to the inclusion of the particular characteristics of the distillation curve. Two approaches were used to estimate the CCI4737 of blends (see Fig. 9). In the rst, this parameter was calculated from values of blend densities at 15 C and distillation curve points obtained from Kays mixing rule. In the second case, it was estimated directly from the mixing rule as a function of biodiesel content and the value of the parameter for pure fuels. As can be seen in Fig. 9, the results obtained using both approaches are similar and indicate that CCI increases with biodiesel content. 4. Conclusions Basic properties of palm oil biodieseldiesel fuel blends were measured according to ASTM standards. Experimental data showing the variation of density and kinematic viscosity with temperature were properly tted by means of statistical regressions. According to the low values obtained for the absolute average deviations, it was found that simple mixing rules

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[22] ASTM D86-05. Standard test method for distillation of petroleum products at atmospheric pressure, Philadelphia, 2005. [23] ASTM D976. Standard test method for calculated cetane index of distillate fuels, Philadelphia, 2005. [24] ASTM D4737-04. Standard test method for calculated cetane index by four variable equation, Philadelphia, 2005. [25] Kerschbaum S, Rinke G. Measurement of the temperature dependent viscosity of biodiesel fuels. Fuel 2003;83:28791. [26] Allen CAW, Watts KC, Ackman RG, Pegg MJ. Predicting the viscosity of biodiesel fuels from their fatty acid ester composition. Fuel 1999;78:131926. [27] CHEVRON PRODUCTS COMPANY. Diesel Fuels Technical Review (FTR-2), 1998. [28] Fonn CS, May CY, Liang YC, Ngan MA, Basiron Y. Palm biodiesel: gearing towards Malaysian standards. Palm oil Dev 2005; 42:2834.