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LIQUID-LIQUID EQUILIBRIUM FOR TERNARY SYSTEMS CONTAINING ETHYLIC BIODIESEL + ANHYDROUS ETHANOL + REFINED VEGETABLE OIL (SUNFLOWER OIL, CANOLA OIL AND PALM OIL): EXPERIMENTAL DATA AND THERMODYNAMIC MODELING

Abstract

Phase equilibria of the reaction components are essential data for the design and process operations of biodiesel production. Despite their importance for the production of ethylic biodiesel, the reaction mixture, reactant (oil and ethanol) and the product (fatty acid ethyl esters) up to now have received less attention than the corresponding systems formed during the separation and purification phases of biodiesel production using ethanol. In this work, new experimental measurements were performed for the liquid-liquid equilibrium (LLE) of the system containing vegetable oil (sunflower oil and canola oil) + ethylic biodiesel of refined vegetable oil + anhydrous ethanol at 303.15 and at 323.15 K and the system containing refined palm oil + ethylic biodiesel of refined palm oil + ethanol at 318.15 K. The experimental data were successfully correlated by the nonrandom two-liquid (NRTL) model; the average deviations between calculated and experimental data were smaller than 1.00%.

Keywords:
Ethylic biodiesel; Liquid-liquid equilibrium; Sunflower oil; Canola oil; Palm oil; Ethanol; NRTL model

INTRODUCTION

Biodiesel, a clean renewable, biodegradable, and nontoxic fuel, has recently been considered as the best candidate for diesel fuel substitution because it can be used in any compression ignition engine without the need of modification. Ethylic biodiesel produced from some vegetable oils and ethanol is entirely based on renewable agricultural sources. In relation to methanol, ethanol has a superior dissolving capability, lower toxicity, higher heat content, higher cetane index and lower cloud and pour points and it is produced in large quantities from sugar cane in Brazil. Although there is an emphasis on production of biofuel made of soybean oil, the other vegetable oils such as sunflower, canola and palm have the potential to produce biodiesel (Porte et al., 2010Porte, A. F., Schneider, R. D. D., Kaercher, J. A., Klamt, R. A., Schmatz, W. L., Da Silva, W. L. T., Severo, W. A., Sunflower biodiesel production and application in family farms in Brazil. Fuel, 89, 3718-3724 (2010).; Stamenkovic et al., 2011Stamenkovic, O. S., Velickovic, A. V., Veljkovic, V. B., The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. Fuel, 90, 3141-3155 (2011).).

Biodiesel is a mixture of fatty acid esters that is industrially produced through the transesterification reaction of a vegetable oil or a fat with an alcohol, usually using a basic catalyst (Issariyakul and Dalai, 2014Issariyakul, T., Dalai, A. K., Biodiesel from vegetable oils. Renewable and Sustainable Energy Reviews, 31, 446-471 (2014).).

The phase equilibria of the reaction components are very important for ethylic biodiesel production. The transesterification shows a complex phase behavior, forming two phases initially due to the fact that the reactants (ethanol and vegetable oil) are partially miscible, as demonstrated by Follegatti-Romero et al. (2010b)Follegatti-Romero, L. A., Lanza, M., Da Silva, C. A. S., Batista, E. A. C., Meirelles, A. J. A., Mutual solubility of pseudobinary systems containing vegetable oils and anhydrous ethanol from (298.15 to 333.15) K. Journal of Chemical and Engineering Data, 55, 2750-2756 (2010b).. In the presence of a catalyst, the reaction mixture changes slowly into a fatty acid ethyl ester (biodiesel)-ethanol-vegetable oil-glycerol mixture, forming a partially miscible system.

The solubility of ethanol in the vegetable oil and fatty acid ethyl ester (FAEE) can greatly influence the reaction rate during the production of biodiesel. Consequently, the composition and the prediction of the reactant distributions between the immiscible phases in several conditions are required to design and to operate chemical reactors destined for ethylic biodiesel production.

Liquid-liquid equilibrium (LLE) data for systems containing fatty acid ethyl esters, vegetable oils and ethanol have recently been the focus of several research works. Liu et al. (2008)Liu, X. J., Piao, X. L., Wang, Y. J., Zhu, S. L., Liquid-liquid equilibrium for systems of (fatty acid ethyl esters plus ethanol plus soybean oil and fatty acid ethyl esters plus ethanol plus glycerol). Journal of Chemical and Engineering Data, 53, 359-362 (2008). determined experimentally the LLE data for fatty acid ethyl esters + ethanol + soybean oil from 300.15 to 343.15 K. Mesquita et al. (2011)Mesquita, F. M. R., Feitosa, F. X., Sombra, N. E., De Santiago-Aguiar, R. S., De Sant'ana, H. B., Liquid-liquid equilibrium for ternary mixtures of biodiesel (soybean or sunflower) plus glycerol plus ethanol at different temperatures. Journal of Chemical and Engineering Data, 56, 4061-4067 (2011). measured the LLE of biodiesel (from soybean or sunflower oils) + glycerol + ethanol at different temperatures and compared the experimental data with the ones calculated from the NRTL model. Finally, Follegatti-Romero et al. (2010b) measured the mutual solubility of soybean oil, sunflower oil, rice bran oil, cottonseed oil, palm olein and palm oil with anhydrous ethanol from 298.15 K to 333.15 K. Silva et al. (2010)Da Silva, C. A. S., Sanaiotti, G., Lanza, M., Follegatti-Romero, L. A., Meirelles, A. J. A., Batista, E. A. C., Mutual solubility for systems composed of vegetable oil plus ethanol plus water at different temperatures. Journal of Chemical and Engineering Data, 55, 440-447 (2010). measured the mutual solubility of canola oil, corn oil, macauba oil and Jatropha curcas oil with ethanol and water at different temperatures. However, the data for the ternary system containing a mixture of ethylic biodiesel, ethanol and vegetable oil is still scarce in literature.

The objective of this work was to increase the available liquid-liquid equilibrium data for systems containing fatty acid ethyl esters, ethanol and refined vegetable oils of interest for the production of ethylic biodiesel, in particular the equilibrium data for systems containing refined vegetable oil (sunflower oil and canola oil) + ethylic biodiesel of vegetable oil + anhydrous ethanol at 303.15 and at 323.15 K and a system containing refined palm oil + ethylic biodiesel of palm oil + ethanol at 318.15 K.

EXPERIMENTAL SECTION

Materials

Anhydrous ethanol and the glacial acetic acid were purchased from Merck (Germany), with purities of 99.5% and 99.0%, respectively. Tetrahydrofuran (THF) was purchased from Tedia (USA), with a purity of 99.8% and sodium ethoxide, from Sigma Aldrich (USA), with a purity of 99%.

Refined sunflower and canola oils were purchased from Bunge (São Paulo/SP, Brazil) and palm oil was provided by Agropalma (Belém/PA, Brazil). The fatty acid compositions of the vegetable oils studied in this work are presented in Table 1. These compositions were determined by gas chromatography of the fatty acid methyl esters using the official AOCS method (1-62) (Aocs, 1988). Prior to the chromatographic analysis, the fatty acids of the samples were transformed into the respective fatty acid methyl esters using the method of Hartman and Lago (1973)Hartman, L., Lago, R. C., Rapid preparation of fatty acid methyl esters from lipids. Lab Pract, 22, 475-6 passim (1973).. From the fatty acid compositions, the probable triacylglycerol compositions of the vegetable oil were calculated using the algorithm suggested by Antoniosi Filho et al. (1995)Antoniosi, N. R., Mendes, O. L., Lancas, F. M., Computer-prediction of triacylglycerol composition of vegetable-oils by HRGC. Chromatographia, 40, 557-562 (1995).. In order to calculate the probable triacylglycerol compositions, the quantities of trans isomers (see Table 1) were computed with their respective cis isomers. In Table 1, the main triacylglycerol represents the component with the greatest composition in the isomer set with x carbons and y double bonds. The results shown allow the calculation of the average molar masses of the sunflower oil, canola oil and palm oil. The values obtained were 877.61 g mol-1, 881.77 g mol-1, and 851.81 g mol-1, respectively.

Table 1
Fatty acid compositions of the vegetable oils.

Fatty acid ethyl ester compositions of biodiesels were determined in triplicate using the official AOCS method (1-62) (Aocs, 1988AOCS, American Oil Chemists' Society, Official Methods and Recommended Practices of the AOCS. AOCS Press. Champaing (1988).). In Table 2, the compositions of biodiesel studied in this work are presented. From these compositions (Table 2), the average molar masses of biodiesels from sunflower oil, from canola oil and from palm oil were calculated and the values found were 307.24, 309.26 and 299.10 g mol-1, respectively.

Table 2
Fatty acid ethyl ester compositions of biodiesels.

For the fitting process of the thermodynamic model, the vegetable oils and biodiesels were treated as a respective single triacylglycerol and a single fatty acid ethyl ester (FAEE) with the calculated average molar masses.

Apparatus and Procedures

The liquid-liquid equilibrium data for the systems containing vegetable oils (sunflower oil and canola oil) + ethylic biodiesels of the vegetable oil + anhydrous ethanol were determined at 303.15 and at 323.15 K and the system containing refined palm oil + ethylic biodiesel of the palm oil + ethanol was determined at 318.15 K.

Tie lines were determined using sealed headspace glass tubes (20 mL) (Perkin Elmer) by the same procedure described by Basso et al. (2012). After addition of the compounds into the vial, this was sealed and vigorously stirred (Phoenix, model AP 56, Araraquara, Brazil) and conditioned in a thermostatic bath (Cole Parmer, model 12101-55, Chicago, USA) for temperature control. After approximately 24 hours, two clean and transparent phases with a well defined interface are formed. Sample of the two phases, a phase rich in vegetable oil and a phase rich in ethanol, were collected with the help of syringes and diluted in tetrahydrofuran immediately after the collection, as described by Follegatti-Romero et al. (2012a)Follegatti-Romero, L. A., Oliveira, M. B., Batista, F. R. M., Batista, E. A. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibria for ternary systems containing ethyl esters, ethanol and glycerol at 323.15 and 353.15 K. Fuel, 94, 386-394 (2012a)..

Samples of the two phases were analyzed by High Pressure Size Exclusion Chromatography (HPSEC) using the same procedure described by Follegatti-Romero et al. (2012a)Follegatti-Romero, L. A., Oliveira, M. B., Batista, F. R. M., Batista, E. A. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibria for ternary systems containing ethyl esters, ethanol and glycerol at 323.15 and 353.15 K. Fuel, 94, 386-394 (2012a)..

The reliability of the tie lines obtained from the experimental data was checked according to the procedure proposed by Marcilla et al. (1995)Marcilla, A., Ruiz, F., Garcia, A. N., Liquid-liquidsolid equilibria of the quaternary system waterethanol-acetone-sodium chloride at 25-degrees-C. Fluid Phase Equilibria, 112, 273-289 (1995)., recently used by Follegatti-Romero et al. (2012b)Follegatti-Romero, L. A., Oliveira, M. B., Batista, E. A. C., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibria for ethyl esters plus ethanol plus water systems: Experimental measurements and CPA EoS modeling. Fuel, 96, 327-334 (2012b)., Basso et al. (2012)Basso, R. C., Meirelles, A. J. D., Batista, E. A. C., Liquid-liquid equilibrium of pseudoternary systems containing glycerol plus ethanol plus ethylic biodiesel from crambe oil ( Crambe abyssinica ) at T/K = (298.2,318.2,338.2) and thermodynamic modeling. Fluid Phase Equilibria, 333, 55-62 (2012). and Ansolin et al. (2013)Ansolin, M., Basso, R. C., Meirelles, A. J. D., Batista, E. A. C., Experimental data for liquid-liquid equilibrium of fatty systems with emphasis on the distribution of tocopherols and tocotrienols. Fluid Phase Equilibria, 338, 78-86 (2013).. According to Marcilla et al. (1995)Marcilla, A., Ruiz, F., Garcia, A. N., Liquid-liquidsolid equilibria of the quaternary system waterethanol-acetone-sodium chloride at 25-degrees-C. Fluid Phase Equilibria, 112, 273-289 (1995)., global mass balance deviations less than 0.5% ensure the good quality of the experimental data.

Thermodynamic Modeling

The experimental data determined were used to adjust the parameters of the NRTL model. The model in terms of mass fractions was used in the objective function instead of mole fractions due to the large difference in molar masses between vegetable oils and ethanol. This approach was also applied by Follegatti-Romero et al. (2010)Follegatti-Romero, L. A., Lanza, M., Batista, F. R. M., Batista, E. A. C., Oliveira, M. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibrium for ternary systems containing ethyl esters, anhydrous ethanol and water at 298.15, 313.15, and 333.15 K. Industrial & Engineering Chemistry Research, 49, 12613-12619 (2010a). and Lanza et al. (2008)Lanza, M., Neto, W. B., Batista, E., Poppi, R. J., Meirelles, A. J. A., Liquid-liquid equilibrium data for reactional systems of ethanolysis at 298.3 K. Journal of Chemical and Engineering Data, 53, 5-15 (2008).. In this case, the NRTL-model is expressed as follows:

where:

Aij , Aji and αij are the adjustable interaction parameters between the pair of components i and j , C is the number of components and T is the absolute temperature.

The estimation of the interaction parameters was performed by using a flash liquid-liquid calculation implemented in Fortran code TML-LLE 2.0 following the same procedure utilized by Stragevitch & d´Ávila (1997)Stragevitch, L., D´Ávila, S. G. Application of a generalized maximum likelihood method in the reduction of multicomponent liquid-liquid equilibrium data. Brazilian Jounal of Chemical Engineering, 14, 41-52 (1997)..

The average deviations (δ) between the experimental compositions and those estimated by the NRTL model were calculated according to Eq. (5).

N is the total number of tie lines of the corresponding system, C is the total number of components (C=3), the superscripts OP and EP represent the oil rich phase and ethanol rich phase , respectively. The subscript i is the component and n stands for the tie line number and the superscripts exptl and calcd refer to the experimental and calculated compositions, respectively.

RESULTS AND DISCUSSION

Liquid-liquid equilibrium data at 9.42.105 Pa approximately for refined vegetable oil (sunflower oil or canola oil) + ethylic biodiesel of the refined vegetable oil + anhydrous ethanol systems were measured at 303.15 and at 323.15 K. The system containing refined palm oil + ethylic biodiesel of the palm oil + ethanol was studied at 318.15 K.

Tables 3, 4 and 5 present the overall compositions and the corresponding tie lines for the pseudoternary systems composed of refined sunflower oil (1) + ethylic biodiesel of the refined sunflower oil (4) + anhydrous ethanol (7); refined canola oil (2) + ethylic biodiesel of the refined canola oil (5) + anhydrous ethanol (7); and refined palm oil (3) + ethylic biodiesel of the refined palm oil (6) + anhydrous ethanol (7).

Table 3
Experimental liquid-liquid equilibrium data for the pseudoternary system containing refined sunflower oil (1) + ethylic biodiesel of the refined sunflower oil (4) + anhydrous ethanol (7) at 303.15 K and 323.15 K.
Table 4
Experimental liquid-liquid equilibrium data for the pseudoternary system containing refined canola oil (2) + ethylic biodiesel of the refined canola oil (5) + anhydrous ethanol (7) at 303.15 K and 323.15 K.
Table 5
Experimental liquid-liquid equilibrium data for the pseudoternary system containing refined palm oil (4) + ethylic biodiesels of the refined palm oil (6) + anhydrous ethanol (7) at 318.15 K.

The deviations of the global mass balance for all systems studied were less than 0.5%, ensuring the quality of the experimental data.

Figure 1 shows the ternary diagrams of systems composed of refined sunflower oil (1) + biodiesel of the refined sunflower oil (4) + ethanol (7), refined canola oil (2) + biodiesel of the refined canola oil (5) + anhydrous ethanol (7) at 303.15 K and 323.15 K and the systems composed of refined palm oil (3) + biodiesel of the refined palm oil (6) + ethanol (7) at the 318.15 K,

Figure 1
Liquid-liquid equilibrium for the system containing (A) refined sunflower oil (1) + ethylic biodiesel of the refined sunflower oil (4) + ethanol (7) at 303.15 K (---●---) and at 323.15 K(―■―); (B) refined canola oil (2) + ethylic biodiesel of the refined canola oil (5) + ethanol (7) at 303.15 K (---●---) and at 323.15 K (―■―) and (C) refined palm oil (3) + biodiesel of the refined palm oil (6) + ethanol (7) at 318.15 K (―■―).

The solubility of the oil-rich phase and the ethanol-rich phase was enhanced by the increase of the temperature in the systems studied at different temperatures. In Figure 1 (A) and 1 (B), it can be noted that, with the increase in temperature, the solubility between both phases increases and the heterogeneous area decreases. Figure 1 (B) shows that biodiesel of canola oil has a slight preference for the oil-rich phase. The opposite behavior can be observed in Figure 1 (A) and 1 (C), where the ethylic biodiesel of sunflower oil and ethylic biodiesel of palm oil, respectively, have a slight preference for the ethanol-rich phase. From this figure, a good alignment can also be observed in the experimental data, relative to the overall and to the two phase compositions.

Table 6 shows the binary interaction parameters adjusted for the NRTL model for the systems composed of refined sunflower oil (1) + ethylic biodiesel of the sunflower oil (4) + anhydrous ethanol (7), refined canola oil (2) + ethylic biodiesel of the canola oil (5) + anhydrous ethanol (7) at 303.15 K and at 323.15 K and refined palm oil (3) + ethylic biodiesel of the palm oil (6) + anhydrous ethanol (7) at 318.15 K. The average deviations between the experimental and calculated composition for these systems are shown in Table 7.

Table 6
Parameters of the NRTL model for the systems composed of refined sunflower oil (1) + ethylic biodiesel of the sunflower oil (4) + anhydrous ethanol (7), refined canola oil (2) + ethylic biodiesel of the canola oil (5) + anhydrous ethanol (7) at 303.15 K and at 323.15 K and refined palm oil (3) + ethylic biodiesel of the palm oil (6) + anhydrous ethanol (7) at 318.15 K.
Table 7
Average deviations between the experimental and calculated phase compositions of the systems.

According to the values of the average deviations between experimental and calculated phase composition of the systems presented in Table 7, the thermodynamic model was able to accurately describe the phase compositions of the systems studied in this work. Follegatti-Romero et al. (2010a)Follegatti-Romero, L. A., Lanza, M., Batista, F. R. M., Batista, E. A. C., Oliveira, M. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibrium for ternary systems containing ethyl esters, anhydrous ethanol and water at 298.15, 313.15, and 333.15 K. Industrial & Engineering Chemistry Research, 49, 12613-12619 (2010a). and Silva et al. (2010)Da Silva, C. A. S., Sanaiotti, G., Lanza, M., Follegatti-Romero, L. A., Meirelles, A. J. A., Batista, E. A. C., Mutual solubility for systems composed of vegetable oil plus ethanol plus water at different temperatures. Journal of Chemical and Engineering Data, 55, 440-447 (2010). found values for deviations between experimental and calculated liquid-liquid equilibrium data similar to those found in this work.

The good adjustment of the parameters of the NRTL model can be viewed in the ternary diagram shown in Figure 2. This figure represents the good agreement between experimental and calculated data.

Figure 2
NRTL model correlations and experimental data for the systems composed of: (A) refined sunflower oil (1) + ethylic biodiesel of the refined sunflower oil (4) + anhydrous ethanol (7) at 303.15 K: (B) refined canola oil (2) + ethylic biodiesel of the refined canola oil (5) + anhydrous ethanol (7) at 303.15 K: (―■―) experimental data; (-----) NRTL model.

CONCLUSIONS

Liquid-liquid equilibrium data for the pseudoternary systems containing vegetable oil + ethylic biodiesel of the vegetable oil + anhydrous ethanol were obtained at different temperatures. From the results obtained, it was found that the solubilities of the systems were affected by temperature and concentration of biodiesels.

The average deviations between the experimental data and the compositions calculated by NRTL presented values between 0.55% and 1.00%, representing a good description in LLE of these systems.

ACKNOWLEDGMENTS

The authors wish to acknowledge Agropalma (Belém/PA, Brazil) for kindly supplying the refined palm oil, and CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico, 483340/2012- 0, 305870/2014-9 and 406856/2013-3) and FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo, 2008/56258-8 and 2012/09646-8) for the financial support.

REFERENCES

  • Ansolin, M., Basso, R. C., Meirelles, A. J. D., Batista, E. A. C., Experimental data for liquid-liquid equilibrium of fatty systems with emphasis on the distribution of tocopherols and tocotrienols. Fluid Phase Equilibria, 338, 78-86 (2013).
  • Antoniosi, N. R., Mendes, O. L., Lancas, F. M., Computer-prediction of triacylglycerol composition of vegetable-oils by HRGC. Chromatographia, 40, 557-562 (1995).
  • AOCS, American Oil Chemists' Society, Official Methods and Recommended Practices of the AOCS. AOCS Press. Champaing (1988).
  • Basso, R. C., Meirelles, A. J. D., Batista, E. A. C., Liquid-liquid equilibrium of pseudoternary systems containing glycerol plus ethanol plus ethylic biodiesel from crambe oil ( Crambe abyssinica ) at T/K = (298.2,318.2,338.2) and thermodynamic modeling. Fluid Phase Equilibria, 333, 55-62 (2012).
  • Da Silva, C. A. S., Sanaiotti, G., Lanza, M., Follegatti-Romero, L. A., Meirelles, A. J. A., Batista, E. A. C., Mutual solubility for systems composed of vegetable oil plus ethanol plus water at different temperatures. Journal of Chemical and Engineering Data, 55, 440-447 (2010).
  • Follegatti-Romero, L. A., Lanza, M., Batista, F. R. M., Batista, E. A. C., Oliveira, M. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibrium for ternary systems containing ethyl esters, anhydrous ethanol and water at 298.15, 313.15, and 333.15 K. Industrial & Engineering Chemistry Research, 49, 12613-12619 (2010a).
  • Follegatti-Romero, L. A., Lanza, M., Da Silva, C. A. S., Batista, E. A. C., Meirelles, A. J. A., Mutual solubility of pseudobinary systems containing vegetable oils and anhydrous ethanol from (298.15 to 333.15) K. Journal of Chemical and Engineering Data, 55, 2750-2756 (2010b).
  • Follegatti-Romero, L. A., Oliveira, M. B., Batista, F. R. M., Batista, E. A. B., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibria for ternary systems containing ethyl esters, ethanol and glycerol at 323.15 and 353.15 K. Fuel, 94, 386-394 (2012a).
  • Follegatti-Romero, L. A., Oliveira, M. B., Batista, E. A. C., Coutinho, J. A. P., Meirelles, A. J. A., Liquid-liquid equilibria for ethyl esters plus ethanol plus water systems: Experimental measurements and CPA EoS modeling. Fuel, 96, 327-334 (2012b).
  • Hartman, L., Lago, R. C., Rapid preparation of fatty acid methyl esters from lipids. Lab Pract, 22, 475-6 passim (1973).
  • Issariyakul, T., Dalai, A. K., Biodiesel from vegetable oils. Renewable and Sustainable Energy Reviews, 31, 446-471 (2014).
  • Lanza, M., Neto, W. B., Batista, E., Poppi, R. J., Meirelles, A. J. A., Liquid-liquid equilibrium data for reactional systems of ethanolysis at 298.3 K. Journal of Chemical and Engineering Data, 53, 5-15 (2008).
  • Liu, X. J., Piao, X. L., Wang, Y. J., Zhu, S. L., Liquid-liquid equilibrium for systems of (fatty acid ethyl esters plus ethanol plus soybean oil and fatty acid ethyl esters plus ethanol plus glycerol). Journal of Chemical and Engineering Data, 53, 359-362 (2008).
  • Marcilla, A., Ruiz, F., Garcia, A. N., Liquid-liquidsolid equilibria of the quaternary system waterethanol-acetone-sodium chloride at 25-degrees-C. Fluid Phase Equilibria, 112, 273-289 (1995).
  • Mesquita, F. M. R., Feitosa, F. X., Sombra, N. E., De Santiago-Aguiar, R. S., De Sant'ana, H. B., Liquid-liquid equilibrium for ternary mixtures of biodiesel (soybean or sunflower) plus glycerol plus ethanol at different temperatures. Journal of Chemical and Engineering Data, 56, 4061-4067 (2011).
  • Porte, A. F., Schneider, R. D. D., Kaercher, J. A., Klamt, R. A., Schmatz, W. L., Da Silva, W. L. T., Severo, W. A., Sunflower biodiesel production and application in family farms in Brazil. Fuel, 89, 3718-3724 (2010).
  • Stamenkovic, O. S., Velickovic, A. V., Veljkovic, V. B., The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. Fuel, 90, 3141-3155 (2011).
  • Stragevitch, L., D´Ávila, S. G. Application of a generalized maximum likelihood method in the reduction of multicomponent liquid-liquid equilibrium data. Brazilian Jounal of Chemical Engineering, 14, 41-52 (1997).

Publication Dates

  • Publication in this collection
    Sept 2015

History

  • Received
    14 Apr 2014
  • Reviewed
    19 Mar 2015
  • Accepted
    20 Mar 2015
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