ARTICLE IN PRESS

BIOMASS AND BIOENERGY

32 (2008) 892 895

Available at www.sciencedirect.com

http://www.elsevier.com/locate/biombioe

Short communication

Esterication of free fatty acids using sulfuric acid as catalyst in the presence of triglycerides
J.M. Marchetti, A.F. Errazu
Planta Piloto de Ingeniera Qumica (UNS-CONICET), Camino La Carrindanga Km. 7, 8000 Baha Blanca, Argentina

ar t ic l e i n f o
Article history: Received 28 March 2007 Received in revised form 21 December 2007 Accepted 8 January 2008 Available online 4 March 2008 Keywords: Esterication Homogeneous catalyst Free fatty acids

abs tra ct
Biodiesel is one of the new possible substitutes of regular fuel for engines and is produced from different vegetable oils or animal fats. The main reaction involved is the transesterication of triglycerides into esters. When an acid oil, such as spent or waste oil, is used, the amount of free fatty acids range from 3% to 40%, and another reaction takes place simultaneously with the transesterication, the direct esterication of the free fatty acid. In this work, the direct esterication reaction of triglycerides to biodiesel was studied and the effects of the main variables involved in the process, reaction temperature, amount of catalyst, initial amount of free fatty acid and the molar ratio alcohol/oil, were analyzed. For this investigation, we employed a model acid oil produced by mixing pure oleic acid with rened sunower oil. Ethanol was used in the experiments instead of methanol since it is less toxic and safer to handle. Sulfuric acid was employed as catalyst because of its advantages compared with conventional homogeneous catalysts (NaOH). It was found that ethanol and sulfuric acid were suitable to perform not only the transesterication reaction but also the direct esterication reaction to increase biodiesel production of the process. & 2008 Elsevier Ltd. All rights reserved.

1.

Introduction

Vegetable oils were initially tested by Rudolph diesel as possible fuel sources for the engine he developed in 1892. Today, because of the incitements from increasing petroleum prices, biodiesel (alkyl esters from vegetable oils or animal fats, dened by ASTM) is used as a substitute of the regular diesel. A great number of advantages are obtained by using biodiesel instead of normal diesel, namely, lower emission of CO due to a better combustion, a better lubricating effect on engines, non-sulfur emission and non-particulate matter pollutants [14].

Over the last years, spent oils have become one of the attractive resources for biodiesel production since it is much cheaper than rened or crude oil and constitute a renewable and sustainable source of energy. This feedstock has a high amount of free fatty acid (FFA), much higher than the maximum amount suitable to be used with basic homogeneous catalysts, which would otherwise result in high amounts of soap produced simultaneously with the transesterication reaction [3,59]. Therefore, to avoid this reaction, alternative technologies should be employed, for example with a homogeneous acid catalyst, solid resins, enzymes or in supercritical process [2,3,5,6,1017].

Corresponding author. Tel.: +54 291 4529537x267; fax: +54 291 4861600.

E-mail address: jmarchetti@plapiqui.edu.ar (J.M. Marchetti). 0961-9534/$ - see front matter & 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.biombioe.2008.01.001

ARTICLE IN PRESS
BIOMASS AND BIOENERGY

32 (2008) 892 895

893

Nomenclature a ASTM C FFA W acidity index American Standard for Testing Materials concentration measured by titration, mol/l free fatty acid, measurement as w/w to the rened oil weight of the sample, mg

N Mw S TG V xffa

molar ratio of alcohol to acid oil molecular weight of the solution, g/mol percentage ratio between mass of catalyst and rened oil triglycerides volume of solution employed for titration, ml conversion of free fatty acid

When acid oils are used to produce biodiesel, the direct esterication of the FFA occurs simultaneously with the transesterication. The direct esterication reaction is important since it will increase the biodiesel production, but also because it will affect the properties of the nal biodiesel fuel [8,11,14]. Both reactions can be summarized as follows [6,9]:

from the oil phase. To improve the separation of the phases, the samples were centrifuged for 20 min. A weighted amount of the sample was dissolved in ethanol and sulfuric ether to make titration analyses, which will determine the remaining FFA. Phenolphthalein was used as indicator. The titration was done with a 0.02 N alkaline solution of KOH. The amount of KOH consumed was registered and acidity was calculated using the following equation: a V 1000 Mw C , W (3)

(1)

R2COOH R4 OH
FFA

Catalyst

Alcohol

! H2 O R2CO2OH2 C2R4 ,
Water Ester

(2)

where R, R1, R2, R3 and R4 denotes any hydrocarbon chain. Since both reactions are equilibrium reactions, the molar relation of alcohol/oil should be over the stoichemetric amount to be able to have a good nal conversion of the FFA as well as of the triglyceride (TG). In this work, the direct esterication reaction of the FFAs in the presence of TGs was studied using a model acid oil. Sulfuric acid was used as catalyst and ethanol was used as alcohol instead of methanol since ethanol is safer to handle, and if ethanol is employed, the nal fuel product can be considered 100% natural and renewable.

where a is the acidity index; C the concentration measured by titration, mol/l; W the weight of the sample, mg; Mw the molecular weight of the solution, g/molg; V the volume of solution employed for titration, ml; xffa the conversion of FFA. And using the following denition, the conversion of FFA was calculated: xffa ai at , ai (4)

where ai is the initial acidity of the mixture and at is the acidity at a t time. The most relevant variables for the reaction which were studied were:

2.

Experimental

   

Reaction temperature. Alcohol to acid oil ratio. Amount of catalyst in relation to the amount of rened oil. Amount of initial FFAs.

To carry out this research, sulfuric acid (98%) was used as catalyst for biodiesel production. A mix of rened sunower oil with pure oleic acid was used to make a model acid oil. Anhydrous ethanol was used as alcohol in order to obtain a fuel that would be considered 100% natural and renewable; however, it is important to notice that the kinetics is different for each alcohol and this will also affect the nal conversion. All these products were provided by Sigma-Aldrich or Anedra. The model acid constituted 10.684% FFA and 89.316% TGs. A lab-scale reactor of 500 ml with mechanic agitation was used; the system contained a warmer jacket that allowed us to set the temperature with an error of 70.1 1C. The oil fed into the reactor was preheated before the catalyst and the alcohol was added. After reaching the reaction temperature, the catalyst and the alcohol were adjoined in the reactor to start the experiment. Samples taken from the reactor were washed with water to stop the reaction and to separate the catalyst and the alcohol

3.
3.1.

Results and discussion

Effects of varying the ratio of alcohol to acid oil (N)

The variation of the FFA conversion for three different amounts of initial quantity of alcohol is shown in Fig. 1. The reaction temperature was set at 45 1C and the agitation speed at 200 rpm. The acid oil used for this reaction had an initial percentage of FFA 10.684%, and S 2.3%. When the molar ratio of alcohol to acid oil was low (Fig. 1), the reaction occurred faster but reached a lower nal conversion compared with when a higher molar ratio was used (Fig. 1). In the latter case, the nal conversion reached was higher, but the initial reaction rate was slow. This non-common behavior is due to a dissolution vs. kinetics effect. For short times, when the amount of alcohol is

ARTICLE IN PRESS
894
BIOMASS AND BIOENERGY

32 (2008) 892 895

1 Conversion of FFA 0.75 0.5 0.25 0 0 50 100 150 200 Time [min] 250 300 350

Conversion of FFA

0.75

0.5

0.25

0 0 50 150 100 Time [min] 200 250

Fig. 1 Effect of different amounts of alcohol. (K) N 10.052, () N 6.126, (m) N 4.212.

Fig. 3 Effect of different reaction temperatures. (m) T 35, (E) T 45 and () T 55 1C.
1

1 Conversion of FFA 0.75

Conversion of FFA

0.5 0.25 0 0 50 100 150 Time [min] 200 250 300

0.75 0.5 0.25 0 0 50 100 150 Time [min] 200 250

Fig. 2 Effect of different amounts of catalyst. (K) S 1.026, (m) S 2.261 and () S 5.139% w/w.

high, a dissolution effect of the alcohol over the reaction mixture takes places with a stronger inuence than that provided by the kinetics, producing a smaller reaction rate; however, as time continues, the reaction also continues to take place and the high concentration of alcohol produces that the nal conversion achieved is higher but required a longer reaction time. Contrarily, when small amounts of alcohol are used, the dissolution effect is less intense, but also, because the concentration is lower, the nal conversion achieved is smaller.

Fig. 4 Effect of different amounts of initial FFA. (m) FFA initial 10.684, () FFA initial 27.22 and (K) FFA initial 3.826% w/w.

55 1C, keeping the remaining reactions parameters constant (S 2.261%, N 6.125:1, initial FFA 10.684%, 200 rpm). The results showed that the reaction was typically endothermic; when the temperature increased, the nal conversion increased as well (Fig. 3). This result corroborates those obtained by Trubiano et al. [15] where the reaction of oleic acid and ethanol to produce ethyloleate was carried on using a commercial enzyme as catalyst.

3.2.

Effects of the amount of catalyst (S) 3.4. Effects of the initial amount of free fatty acid

Effects of varying the amount of catalyst were studied at the reaction conditions of N 6.124:1, T 45 1C, initial FFA 10.684% and agitation of 200 rpm. The results are displayed in Fig. 2 and show that the reaction was highly dependent on the amount of catalyst. The effect was most pronounced in relation to the initial reaction rate. The amount of catalyst did not appear to affect the nal conversion since the three reactions has almost the same nal conversion.

3.3.

Effects of the temperature

Since the reaction temperature was also expected to affect the conversion of FFA, we evaluated the reaction at 35, 45 and

Modications in the initial amount of FFA were also studied. Three different acid oils with varying amounts of FFA were made. The FFA of these oils were 3.826%, 10.684% and 27.22%, respectively. The operational temperature was 45 1C and the alcohol/oil molar ratio was kept constant at 6.124:1; the reaction was performed at 200 rpm while the percentage of catalyst (S) was approximately 2.25%. When the initial amount of FFA was increased, the reaction reached a higher nal conversion (Fig. 4). Furthermore, the reaction rate also increased with increasing amount of FFA. These results were to be expected since the reaction is an equilibrium reaction and increasing one of the reactants would displace the equilibrium towards the product.

ARTICLE IN PRESS
BIOMASS AND BIOENERGY

32 (2008) 892 895

895

3.5.

Transesterication of triglycerides

R E F E R E N C E S

Under the operational reactions that have been tested, the transesterication reaction of TGs takes place simultaneously with the esterication reaction. The amount of ester produced comes in a large part form the FFAs and in a smaller amount from the TGs. The operational conditions that have been tested on this work are not the best one, normally a molar ratio of 30:1 should be used [1,16,17] and a reaction temperature of 65 1C is highly recommendable. Employing the previously mentioned operational conditions, a complete reaction of TG with methanol and 1% w/w of sulfuric acid will be achieved in around 70 h [12]. For the operational conditions used in this research, T 45 1C, N 6:1 and 2.2% w/w of catalyst, a conversion of 30% of TGs was reached in 4 h.

4.

Conclusions

In this study, we showed that sulfuric acid is an attractive alternative to produce biodiesel by direct esterication of a spent oil with high amounts of FFA compared with conventional technology using KOH as catalyst. The esterication process that has been studied shows that the amount of FFA was reduced from 10.684% to values around 0.54% w/w. This nal concentration is slightly higher than the recommendable amount [1,5]; however, the amount of soap that might be produced by these FFA if this is fed into an alkaline transesterication reaction is minimum. The variations in temperature showed that the reaction displayed typical endothermic behavior and that changes in the amount of catalyst affected only the initial reaction and resulted in similar nal conversions. When the molar ratio was varied, the amount of FFA consumed showed that an optimum amount of N exists, which will give a high nal conversion with a fast initial reaction rate. If a higher value of N is employed the reaction will be slower but will reach a higher nal conversion. If a lower value of N is used the reaction will be fast but the nal conversion will be low. We conclude that the best operational conditions studied on this work, which will give the best nal conversion with a good reaction rate, are S 2.261%, FFA 10.684%, N 6.126, T 55 1C, reaching a nal conversion of 96%.

[1] Knothe G, Krahl J, Van Gerpen J. The biodiesel handbook. Champaign, IL: AOCS press; 2005. [2] Srivastava A, Prasad R. Triglycerides-based diesel fuels. Renewable & Sustainable Energy Reviews 2000;4:11133. [3] Marchetti JM, Miguel VU, Errazu AF. Possible methods for biodiesel production. Renewable Sustainable Energy Reviews 2007;11:130011. [4] Vicente G, Martinez M, Aracil J. Integrated biodiesel production: a comparison of different homogeneous catalysts systems. Bioresource Technology 2004;92:297305. [5] Ma F, Milford AH. Biodiesel production: a review. Bioresource Technology 1999;70:115. [6] Meher LC, Vidya Sagar D, Naik SN. Technical aspects of biodiesel production by transestericationa review. Renewable and Sustainable Energy Reviews 2006;10(3):24868. [7] Carraretto C, Macor A, Mirandola A, Stoppato A, Tonon S. Biodiesel as alternative fuel: experimental analysis and energetic evaluations. Energy 2004;29:2195211. [8] Knothe G. Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters. Fuel Processing Technology 2005;86:105970. [9] Geller DP, Goodrum JW. Effects of specic fatty acid methyl esters on diesel fuel lubricity. Fuel 2004;83:23516. [10] Marchetti JM, Miguel VU, Errazu AF. Heterogeneous esterication of oil with high amount of free fatty acids. Fuel 2007;86:90610. [11] Perez, Graciela B. Analysis of enzymatic alcoholisis reaction of vegetable oils. PhD thesis, Planta Piloto de Ingeniera Qumica, UNS-CONICET, 2003. [12] Zhang Y, Dube MA, McLean DD, Kates M. Biodiesel production from waste cooking oil: 1. Process design and technological assessment. Bioresource Technology 2003;89:116. [13] Dube MA, Tremblay AY, Liu J. Biodiesel production using a membrane reactor. Bioresource Technology 2007;98:63947. [14] Ramadhas AS, Jayaraj S, Muraleedharan C. Biodiesel production from high FFA rubber seed oil. Fuel 2005;84(4):33540. [15] Trubiano G, Borio D, Errazu A. Inuence of the operating conditions and the external mass transfer limitations on the synthesis of fatty acid esters using a Candida antarctica lipase. Enzyme and Microbial Technology 2007;40:71622. [16] Canakci M, Van Gerpen J. Biodiesel production via acid catalysis. Transactions of the ASAE 2003;42(5):120310. [17] Canakci M, Van Gerpen J. Biodiesel production from oils and fats with high free fatty acids. Transactions of the ASAE 2003;44(6):142936.

Acknowledgments
Jorge Mario Marchetti would like to thank the National Committee of Scientic and Technical Research (CONICET) for nancial support.