Scientica Acta 2, No.

2, 8 11 (2008)

Chemistry Experimental evaluation of the hydroesterication process: production of biodiesel from Canola oil
Immacolata Manco
Dipartimento Chimica Generale, Universit di Pavia , Viale Taramelli 12, 27100 Pavia, Italy, manco.imma@yahoo.it The objective of this work is to optimise biodiesel production, obtained by esterication of the fatty acid derived from hydrolysis of rapeseed oil. Powdered niobic acid (Nb2 O5 .xH2 O) was used as catalyst. The temperature and the mixing velocity remained constant during all reaction. The best conversion yields for the hydrolysis were observed at 300C with 20% of catalyst: at the highest molar ratio the yield was 88.49% and at the lowest molar ratio the yield was 84.53%. The best conversion yield obtained in the esterication was observed working in the excess of methanol and at a temperature of 200C; the concentration of catalyst is only relevant in the rst 40 minutes of reaction. After one hour, even non-catalytic reaction produced high conversions at 200 C.

1 Introduction
Nowadays one of the main problems in the production of biodiesel using rst generation processes is the availability of raw materials and the cost of rened vegetable oils. The process for producing biodiesel from oil is called transesterication. The process is simple and can work at low temperatures and with low cost catalysts, having conversions near to 100%. However, this process has some drawbacks: the separation glycerol / biodiesel is long and costly the cost of feedstocks is about 80% of the biodiesel production cost [1] industrial transesterication process occurs by means of basic homogeneous catalysis always producing soap and demanding rened oils (more expensive than crude ones) to minimise saponication. [2] The research is now geared towards the improvement of chemical and biological processes necessary to achieve second generations biofuels, using waste materials such as exhausted vegetable oils. The objective of this work is to optimise biodiesel production, obtained by esterication of the fatty acid derived from hydrolysis of rapeseed oil. This process can be applied to any fatty feedstock with any acidity or even humidity. In the hydroesterication process, hydrolysis is a chemical reaction between triglycerides and water, producing fatty acids and glycerol (Fig.1). Thus, hydrolysis increases the acidity of the fatty material instead of free fatty acid removal through rening. Moreover, glycerol obtained from hydrolysis is cleaner than one using transesterication process [2]. In hydroesterication, food grade feedstocks produce food grade glycerol. This never occurs in transesterication where glycerol is generated in the presence of signicant amount of salts and methanol. After hydrolysis, fatty acids are estericated with methanol or ethanol producing pure esters. There is no contact between glycerol (removed during hydrolysis) and biodiesel. Water, a by-product in the esterication (Fig. 2) is re-used in the hydrolysis step in a continuous way.
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Scientica Acta 2, No. 2 (2008)

Fig. 1: Diagram of the reaction of hydrolysis.

Fig. 2: Diagram of the esterication reaction.

The highest is the feedstock acidity, the better will be the yield of the process. Thus, beef tallow, chicken fat, pork fat, yellow grease, crude palm oil, crude jatropha oil, can be used and be transformed in international biodiesel standards at yields higher than 98%. Transesterication cannot be efciently applied in these raw materials. About 80% of the biodiesel production cost is ascribed to fatty material costs. Thus, hydroesterication is a choice that can really improve biodiesel feasibility [2].

2 Experimental
2.1 Material and methods All reactions, hydrolysis and esterication, were conducted in a reactor (Parr Instruments Inc. - Model 4842)-type autoclave, consisting of stainless steel volume of 600 ml and maximum pressure up to 10,000 psi job, with a pipe to extract the sample, automatic rotation and heating mantle. Reagents: canola oil: from a grocery store (initial acidity: 0.17%); niobic acid (HY-340): to CBMM (Companhia Brasileira de Minerao e Metalurgia), powder and pellets, it was put in an oven at 150 C. solution of 0.25 N NaOH for titrations is made in the laboratory from NaOH produced by VETEC (cod1137); anhydrous methanol for esterication. The temperature (250, 275, 300C for hydrolysis and 150, 175, 200C for esterication) and the mixing velocity (700 rpm) remained constant during all reaction. The conversion of the reactions were evaluated evaluating the percentage of free fatty acid and calculated by titration with NaOH 0.25 N (Method proposed from AOCS [American Oil Chemists Society) Ca-40]. Additional biodiesel evaluation was carried out according to EN 14214, European biodiesel standard. In the Erlenmeyer ask there are about 1 g of sample, 25 ml of ethanol, 1 ml of phenolphthalein, 3 drops of 0.1 N NaOH, and the title with NaOH 0.25 N[2].
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Scientica Acta 2, No. 2 (2008)

2.2 Hydrolysis The percentage of fatty acid formed during the hydrolysis was calculated by the following equation: Index of acidity (%) = At = (R*V)/Ma Ma = mass of the sample taken V = volume of 0.25 N NaOH used for titration R = value ranging between 6.99 and 7.05 Because the acidity calculated at time t is "contaminated" by water and glycerol, the nal values are calculated by reference to the dry sample. Efciency of Hydrolysis (%) =R= At x {[(As - Au)x 100]/ As} + At At = acidity at the time t As = the dry acidity Au = acidity of the sample 60 min. At the end of the hydrolysis, the fatty acid was separated from glycerol, the catalyst, when used, can be recovered through ltration. 2.3 Esterication The esterications efciency was calculated by the equation: Efciency (%)= [(Abco-Aa)/Abco]*100 Abco = acidity of white sample (taken before the T reactor reaches the value set) Aa = acidity of the sample time t At the end of the reaction the product was centrifuged to separate the catalyst and then it was heated to remove water, which is by-product of the reaction of esterication.

3 Results and discussion

The best yield obtained in the hydrolysis were observed at 300C with 20% of catalyst: at the highest molar ratio (oil:water 1:20) the conversion yield was 88.49% and at the lowest molar ratio (oil:water 1:5) the conversion yield was 84.53%. The best yield obtained in the esterication was observed working with excess methanol (fatty acid: methanol 1:3) and at a temperature of 200C, the concentration of catalyst is only relevant in the rst 40 minutes of reaction. After one hour, even non-catalytic reaction produced high conversion yields at 200 C. Glycerol obtained by hydrolysis is very pure (food grade) and methyl esters obtained in the esterication step comply with European standards.

4 Conclusion
The minimisation of variables (T, C, RM) is a very relevant research, which can be further developed; it would be interesting to study the reactions occurring under conditions of temperature between 260 and 280 C; amount of catalyst between 5-10%, with RM = 1:5, using crude oil. These preliminary results show that the chemical and physical conditions of the two processes (hydrolysis and esterication) allow continuing the implementation of a continuous process. In conclusion, it can be asserted that the process of hydroesterication is a potential alternative to transesterication, but further studies are needed and especially the development of a more advanced technology.
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Scientica Acta 2, No. 2 (2008)

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100,0 90,0 80,0

c o n v e rs io n ( % )

100,0 90,0 80,0

c o n v e rs io n e ( % )

70,0 60,0 50,0 40,0 30,0 20,0 10,0 0,0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 5 R.M. 300C T 20% c at. 20 R.M. 300C T 20% c at.

70,0 60,0 50,0 40,0 30,0 3 R.M. 200C T 0 % c at. 20,0 3 R.M. 200C T 20% c at. 10,0 0,0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 te m p o (m in .)

tim e (m in .)

Fig. 3: Left:best yield of hydrolysis; Right: best yield of esterication.

Acknowledgements I am gratefully acknowledged to prof. Helder Queiroz Pinto Jr., Energy Economics Group, Institute of Economics, Federal University of Rio de Janeiro, and prof. Donato A. G. Aranda, Chemical Eng. Department Federal University of Rio de Janeiro.

References
[1] L. G. Carvalho, P. P. Britto, L. Camacho, J. A. Morsn-Villarreyes, M. G. Montes DOca, D. G. A. Aranda, Produo de Biodiesel utilizando cido graxo de arroz e cido graxo de palma. Anais do XX SICAT Simposio Ibero-Americano de Catlise (2006). [2] D. G. A. Aranda, Novas Tecnologias para a Produo de Biodiesel 3o Seminrio OCB Rio de Janeiro, 25 de outubro de 2007. [3] L. L. L. Rocha, J. A. Gonalves, G. J. Reinaldo, A. K. Domingos, M. Mello, N. R. Antoniossi Filho, D. G. A. Aranda, Produo de cido graxo a partir da reao de hidrlise dos leos de mamona (Ricinus communis L.) e soja (Glycine max).14o Congresso Brasileiro de Catlise Anais do Congresso Brasileiro de Catlise (2007).

2008 Universit degli Studi di Pavia