Fuel 86 (2007) 23832388 www.fuelrst.

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A kinetic study of the esterication of free fatty acids (FFA) in sunower oil
M. Berrios, J. Siles, M.A. Martn *, A. Martn
Departamento de Qumica Inorganica e Ingeniera Qumica, Universidad de Cordoba, Campus Universitario de Rabanales, Edicio Marie Curie, 14071 Cordoba, Spain Received 27 July 2006; received in revised form 2 February 2007; accepted 6 February 2007 Available online 7 March 2007

Abstract The kinetics of the esterication of free fatty acids (FFA) in sunower oil with methanol in the presence of sulphuric acid at concentrations of 5 and 10 wt% relative to free acids as catalyst and methanol/oleic acid mole ratios from 10:1 to 80:1 was studied. The experimental results were found to t a rst-order kinetic law for the forward reaction and a second-order one for the reverse reaction. The inuence of temperature on the kinetic constants was determined by tting the results to the Arrhenius equation. The energy of activation for the forward reaction decreased with increasing catalyst concentration from 50 745 to 44 559 J/mol. Based on the experimental results, a methanol/oleic acid mole ratio of 60:1, a catalyst (sulphuric acid) concentration of 5 wt% and a temperature of 60 C provided a nal acid value for the oil lower than 1 mg KOH/g oil within 120 min. This is a widely endorsed limit for ecient separation of glycerin and biodiesel during production of the latter. 2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Esterication; FFA; Kinetics; Sunower

1. Introduction Transportation is the activity with the most uncertain future as regards energy demands in the European Union. In fact, about 67% of the current oil demand in the EU is estimated to be required by this sector. Because the EU relies heavily on oil imports, fuel consumption is among its primary concerns. Liquid fuels of agricultural origin are being increasingly considered as alternatives to gasoline and gas oil as sources of energy. Specically, biodiesel has a substantial potential to reduce oil imports and ensure continuity in the energy supply. Biodiesel, which consists of long-chain fatty acid methyl ethers (FAME) obtained from renewable lipids such as those in vegetable oils or animal fat, can be used both as

Corresponding author. Tel.: +34 957218586; fax: +34 957218625. E-mail address: iq2masam@uco.es (M.A. Martn).

an alternative fuel and as an additive for petroleum diesel. The prex bio denotes its biological origin and renewable character; by contrast, the better known, non-renewable petroleum diesel is obtained from petroleum distillates. At present, FAME are obtained by reacting triglycerides with lower alcohols such as methanol or ethanol in the presence of a strong base as a catalyst; the reaction yields glycerin as a by-product. The triglycerides used come from a variety of oils including rapeseed, sunower, soybean, palm and peanut oil, as well as from animal fat [13]. The use of these materials, however, is restricted by their high cost, which has led some authors [4] to recommend employing used oil and some animal fats as alternative raw materials. According to several researchers Freedman et al. [5], Liu [6] and Mittelbach et al. [7], the oil or fat used in alkaline transesterication reactions should contain no more than 1% free fatty acids (FFA), which is equivalent to 2 mg KOH/g triglyceride. If the FFA level exceeds this

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.02.002

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M. Berrios et al. / Fuel 86 (2007) 23832388

threshold, saponication hinders separation of the ester from glycerine and reduces the yield and formation rate of FAME. Canakci and Van Gerpen [8] reduces the recommended acidity to below 1 mg KOH/g triglyceride (i.e. a 0.5% FFA content). Van Gerpen [9] found the FAME yield from unrened oil to decrease from 9398% to 8687% in the presence of 6.66% of FFA and ascribed it to phospholipids destroying the catalyst. According to Meher et al. [10], the FFA and moisture contents are the two variables dictating the feasibility of transesterifying vegetable oils. Others researchers [11] studied the transesterication of beef tallow catalysed by NaOH in the presence of free fatty acids and water. The yield of beef tallow methyl esters (BTME) was highest when no FFA or water was added to the reaction mixture. On the other hand, the addition of 0.6% of FFA resulted in the lowest BTME apparent yield (less than 5%), whichever the amount of water supplied. The economic and environmental interest in using oils and fats involved in the production of biodiesel, the unavoidable need to remove FFA and the interest in characterizing the kinetics of the reaction with a view to optimizing the reactor dimensions led us to undertake the present study with a view to examining the inuence of operational variables on the kinetics of esterication of FFA in sunower oil using sulphuric acid as catalyst. 2. Materials and methods The raw material used in the esterication tests was sunower oil the acidity of which was raised by addition of fatty acids obtained in its physical rening. The acid value of the samples ranged from 5 to 7 mg KOH/g oil, which is slightly higher than the levels typically found in frying oils. The sample contained the following major fatty acids: palmitic (6%), stearic (3%), oleic (17%) and linoleic (72%); all were determined by gas chromatography in accordance with UNE-EN 14331. The acid value was determined as per the UNE-55001, following washing of the sample with distilled water to remove any residual catalyst. The esterication catalyst used was sulphuric acid at concentrations of 5 and 10 wt% relative to total acidity (as oleic acid). Free fatty acids (FFA) were esteried with anhydrous methanol, using a methanol/oleic acid mole ratio of 20:1 80:1 and 10:1114:1 with a catalyst concentration of 5% and 10%, respectively. The inuence of temperature on the esterication rate was studied at a xed methanol/oleic acid ratio of 60:1, the two catalyst concentrations and 30, 40, 50 and 60 C. The experimental set-up used was identical with that previously employed by [12], batch stirring reactor of 2 l of capacity with magnetic agitation, except that the heating

system consisted of a jacketed reactor through which water from a thermostated system at the required temperature was circulated. 3. Results and discussion The elimination of FFA relies on the well-known esterication reaction R1 COOH + R2 OH R1 COOR2 + H2 O 1

which is catalysed by acids. In this work, R1 was a linear chain of 1117 carbon atoms containing a variable number of unsaturations depending on the particular origin of the raw material, and R2 was a methyl radical. By means of essays, it has been veried that the esterication reaction does not take place in catalyst absence (Fig. 1). A test has been made with oil which acid value is known, a 5% w/w catalyst concentration and a molar ratio methanol/oleic acid of 240:1. The experiment has been carried out in the same conditions of temperature and agitation that the others tests, for 5 min so that the reaction of esterication does not pass in an appreciable length. Next, the mixture was settled in order to separate the two phases. The acidity of the methanol phase (methanol and catalyst) before and after reaction has been determined: 5,78 and 5,27 mg KOH/g sample, respectively. The smaller obtained value conrms that fatty acids do not dissolve in the methanol phase and the part of catalyst could dissolve in the oil phase. Therefore, the chemical reaction takes place in the oil phase. This reaction is heterogeneous, methanol is only sparsely soluble in sunower oil; so it requires agitation in order to avoid mass transfer taking control over the process [3]. Tests were conducted at variable agitation speeds from 200 to 600 rpm above which this variable was found to have no further eect on the reaction rate (Fig. 2). A speed
2.8 2.6 2.4

Acid value (mg KOH/g oil)

2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0 50 100 150 200 Reaction Non-catalyzed Reaction Catalyzed

Time (min)

Fig. 1. Comparison of the non-catalysed and catalysed reaction.

M. Berrios et al. / Fuel 86 (2007) 23832388

3.5 200 rpm 300 rpm 400 rpm 500 rpm 600 rpm
6

2385

60C; 10% H2SO4

5

Acid value (mg KOH/g oil)

Acid value (mg KOH / g oil)

3.0

10:1 20:1 40:1 60:1 80:1 114,6:1

2.5

2.0

1.5

1.0 0 20 40 60 80 100 120 140

0 0 20 40 60 80 100 120 140

Time (min)

Time (min)

Fig. 2. Comparison of the agitation speeds.

Fig. 4. Variation of the acid value with the methanol/oleic acid mole ratio at a sulphuric acid concentration of 10 wt%.

of 600 rpm was therefore subsequently used to examine the inuence of the catalyst concentration, methanol/fatty acid mole ratio and temperature on the acid value. Being the density of the uid of 913 kg/m3, the diameter of the agitator 4 cm, the speed of agitation of 600 rpm and the power consumed in the process is of 6.6 W, the tests were carried out with a power number of 20 (Np). Figs. 3 and 4 show the variation of the acid value with the methanol/oleic acid mole ratio at a sulphuric acid concentration of 5% and 10%, respectively. In both cases, the reaction rate increased with increasing mole ratio. Above 60:1, however, the increase was negligible, so this ratio was adopted as the experimental limit in order to avoid unnecessarily increasing operational costs and the reactor size. On the other hand, an increased catalyst concentration increased the esterication rate. Thus, at a methanol/oleic acid mole ratio of 20:1, a catalyst concentration of 5% provided an acid value of 4 mg KOH/g oil within 120 min, whereas one of 10% gave 2 mg KOH/g oil in the same time.
8 7

Once a methanol/oleic acid mole ratio of 60:1 was adopted as optimal, the inuence of temperature at the two catalyst concentrations studied was examined. As expected, raising the temperature increased the esterication rate (see Figs. 5 and 6). The highest rate was obtained at 60 C, which is close to the boiling point of methanol at atmospheric pressure. A higher temperature obviously increased the rate further, but required using a pressure above atmospheric level or a more sophisticated experi mental set-up such as that employed by Kocsisova et al. [13]. A reaction time of 120 min, a methanol/oleic acid mole ratio of 60:1, a sulphuric concentration of 5% and a temperature of 60 C provided an acid value below 1 mg KOH/g oil, which is the maximum recommended level for ensuring a good yield of FAME while facilitating their separation from glycerin in the transesterication reaction. In fact, higher acid values result in saponication by reaction with the catalyst, which decreases the surface tension and facilitates emulsication [8].
7

60C; 5% H2SO4

Acid value (mg KOH / g oil)

6 5 4 3 2 1 0 0 20 40 60 80 100

Acid value (mg KOH / g oil)

20:1 40:1 60:1 80:1

5% H 2 SO4 5% H2SO4

60C 50C 40C 30C

0
120 140

20

40

60

80

100

120

140

Time (min)

Time (min)

Fig. 3. Variation of the acid value with the methanol/oleic acid mole ratio at a sulphuric acid concentration of 5 wt%.

Fig. 5. Variation of the acid value with temperature at a sulphuric acid concentration of 5% and a methanol/oleic acid mole ratio of 60:1.

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M. Berrios et al. / Fuel 86 (2007) 23832388

10% H2SO4

30C 40C 50C 60C

Acid value (mg KOH / g oil)

where s  K2 K A0 a 4 a K1 and K b K K2

5 6

0 0 20 40 60 80 100 120 140

Time (min)

Fig. 6. Variation of the acid value with temperature at a sulphuric acid concentration of 10% and a methanol/oleic acid mole ratio of 60:1.

3.1. Kinetic model The kinetic model used in this work relied on the following assumptions: (a) The esterication reaction was a reversible heterogeneous process the rate of which under the operating conditions used was controlled by that of the chemical reaction. (b) The rate of the non-catalysed reaction was negligible relative to the catalysed reaction. (c) The chemical reaction occurred in the oil phase. (d) The methanol/oleic acid mole ratio used was high enough for the methanol concentration to remain constant throughout the process. Under these conditions, the reaction was assumed to be pseudo-homogeneous, rst-order in the forward direction and second-order in the reverse direction, and hence to conform to the following kinetic law: dA K 1 A K 2 C D dt 2

K1 and K2 were determined by trial and error, using variable b values until a plot of the right-hand side of Eq. (4) consisting of a straight line with a negligible intercept was obtained. By way of example, Fig. 7 shows the tting of the experimental data obtained at a methanol/oleic acid mole ratio of 10:1, a catalyst concentration of 10% and a temperature of 60 C. Similar plots were constructed under all other experimental conditions. Fig. 8 shows the kinetic constants obtained as described above. As expected, K1 increased with increasing methanol/oleic acid mole ratio and catalyst concentration; on the other hand, K2 was negligible irrespective of the catalyst concentration, which indicates that the hydrolysis reaction hardly took place. Based on the small value of K2, some authors have proposed tting experimental data to a rst-order kinetic law [13,15]. The inuence of temperature on the specic reaction rate was determined by tting K1 and K2 to the Arrhenius equation, ! DE K A exp 7 RT using plots of ln K as a function of the reciprocal temperature (Figs. 9 and 10). However, both the frequency factor, A, and the energy of activation, DE, were obtained by nonlinear regression, using the software Mathcad v. 12. The results are shown in Table 1. The energy of activation for the forward reaction decreased with increasing catalyst concentration: from 50 745 J/mol with 5% sulphuric acid to 44 559 J/mol with a 10% concentration of the acid.

1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

Ln{[A0+E(-0.5)] / [A0-E(+0.5)]}

where [A] denotes the concentration of FFA in mg KOH/g oil (i.e. the acid value); [C] and [D] are the concentrations of FAME and water, respectively, formed during the reaction, both also referred to 1 g of oil; and K1 and K2 are the kinetic constants for the forward and reverse reaction, respectively. If [D] and [C] are assumed to be zero at the start (t = 0), and A = A0 E (E being the acidity removed), then, according to Carberry [14], dE K 1 A0 E K 2 E2 dt where A0 is the initial concentration of FFA. Integration of Eq. (3) yields A0 E b 1 2 2 K 2 a t ln A0 E b 1 2 3

y = 4,76510-3 + 0,012x r = 0,998

20

40

60

80

100

120

140

Time (min)

Fig. 7. Determination of the kinetic constants by using Eq. (4) at a methanol/oleic acid mole ratio of 10:1, a catalyst concentration of 10% and a temperature of 60 C.

M. Berrios et al. / Fuel 86 (2007) 23832388

0.07 0.06 0.05 0.04 k1 (min-1) (5%) k1 (min-1) (10%) k2 (g/mgmin) (5%) k2 (g/mgmin) 10%)

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Table 1 Energies of activation and frequency factors for the esterication of FFA in sunower oil A K1 K2 K1 K2 (5%) (5%) (10%) (10%) 2.869 10 37.068 3.913 10+5 707.166
+6

E (J/mol) 50745.2 31007.3 44558.8 42761.4

R2 0.999 0.932 0.997 0.932

0.03 0.02 0.01

8
0.00

5% H2SO4

Calculate acid value (mg KOH/ g oil)

20

40

60

80

100

120

10% H2SO4 6

+10%

Molar ratio (Methanol/Oleic Acid)

-10% 4

Fig. 8. Variation of the rate constants with the methanol/oleic acid mole ratio.
-2

5% H2SO4
-4 ln k1

0
-6

ln k

ln k2 -8

Experimental acid value (mg KOH/g oil)

Fig. 11. Comparison of the experimental acid value and that predicted by Eq. (4).

-10

-12 2,95e-3

3,00e-3

3,05e-3

3,10e-3

3,15e-3

3,20e-3

3,25e-3

3,30e-3

3,35e-3

1/T (K )

-1

Fig. 9. Inuence of temperature on the specic reaction rate (Arrhenius equation) at a sulphuric acid concentration of 5 wt%.
-2 ln k1 -4

Finally, the goodness-of-t of the experimental data to the proposed model was assessed by comparing the experimental acid value with the theoretical prediction of Eq. (4) at a methanol/oleic acid mole ratio of 60:1 (see Fig. 11). Three-fourths of the experimental data were reproduced with errors not greater than 10%. 4. Conclusions

10% H2SO4

-6

-8

ln k2

-10

Free fatty acids (FFA) in sunower oil can be eectively removed by esterication with methanol, using a 5% sulphuric acid concentration relative to FFA, a methanol/ oleic acid mole ratio of 60:1, a temperature of 60 C and agitation at a speed of 250 rpm or higher. Under these conditions, the acidity removed, E, expressed as the acid value (mg KOH/g oil), as a function of time (in min) conforms to the following equation: E b1 A0 e2K 2 at 1 2K 2 at 0:5e2K 2 at e 1

ln k

-12

-14 2,95e-3

3,00e-3

3,05e-3

3,10e-3

3,15e-3

3,20e-3

3,25e-3

3,30e-3

3,35e-3

1/T (K-1)

Fig. 10. Inuence of temperature on the specic reaction rate (Arrhenius equation) at a sulphuric acid concentration of 10 wt%.

where a and b have the same meaning as in Eqs. (5) and (6), respectively, and K1 and K2 are calculated by using the data of Table 1 in Eq. (7). Acknowledgements The authors are grateful to the rm Biodiesel de And aluca for funding this work.

The frequency factor for the forward reaction varied similarly to the energy of activation and increased from 2.869 106 to 3.913 106 in raising the catalyst concentration from 5% to 10%.

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M. Berrios et al. / Fuel 86 (2007) 23832388 Proceedings of the alternative energy conference. Michigan (USA): American Society of Agricultural Engineers; 1994. p. 74. Canakci M, Van Gerpen J. Biodiesel production from oils and fats with high free fatty acids. Trans ASAE 2001;44(6):142936. Van Gerpen J. Biodiesel processing and production. Fuel Process Technol 2004. Meher LC, Vidya Sagar D, Naik SN. Technical aspects of biodiesel production by transesterication a review. Renew Sust Energy Rev 2006;10(3):24868. Ma F, Clements LD, Hanna MA. The eect of catalyst, free fatty acids and water on transesterication of beef tallow. Trans ASAE 1998;41(5):12614. Alcantara R, Amores J, Canoira L, Fidalgo E, Franco MJ, Navarro A. Catalytic production of biodiesel from soy-bean oil, used frying oil and tallow. Biomass Bioenergy 2000;18:51527. Kocsisova T, Cvengros J, Lutisan J. High-temperature esterication of fatty acids with methanol at ambient pressure. Eur J Lipid Sci Technol 2005;107:8792. Carberry JJ. Chemical and catalytic reaction engineering. New York: McGraw-Hill; 1976. Sendzikiene E, Makareviciene V, Janulis P, Kitrys S. Kinetics of free fatty acids esterication with methanol in the production of biodiesel fuel. Eur J Lipid Sci Technol 2004;106:8316.

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