Ultrasonics Sonochemistry 14 (2007) 413417 www.elsevier.

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Ultrasonically driven continuous process for vegetable oil transesterication

Carmen Stavarache a, M. Vinatoru
b

a,*

, Y. Maeda b, H. Bandow

a Costin D. Nenitzescu Institute of Organic Chemistry, 060023 Bucharest, P.O. Box 35-108, Romania Department of Environmental Chemistry, Osaka Prefecture University, Gakuen-cho 1-1, Sakai, Osaka 599-8531, Japan

Received 8 July 2006; accepted 6 September 2006 Available online 16 January 2007

Abstract A bench scale continuous process for the manufacture of biodiesel from neat vegetable oils under high power low frequency ultrasonic irradiation was investigated. The experimental studies explored variations in alcoholoil stoichiometry and type of oil. Important parameters such as residence time and reaction volume were considered. The highest conversion was achieved when short residence time was employed. The transesterication under ultrasonic irradiation is mainly inuenced by the residence time in the reactor and alcoholoil molar ratio. 2006 Elsevier B.V. All rights reserved.
Keywords: Biodiesel; Continuous process; Ultrasound; Ultrasonic ow reactor

1. Introduction Biodiesel is appreciated as a future alternative of diesel fuel due to its advantages in reducing the exhaust emission. The production costs are high, thus biodiesel receives government subsidiaries in order to compete on the markets with the petroleum-based fuel. Extensive research has been done to diminish the production costs such as use of waste oil [1,2] various catalysts [35], xed bed reactor [6], continuous production [7,8]. The biodiesel manufacture consists in the transesterication of a triglyceride with an alcohol. The transesterication process is aected by alcohol type, molar ratio of alcohol to oil, type and amount of catalyst, temperature and purity of the reactants [9]. The transesterication of triglycerides with methanol is a heterogeneous reaction and blending together the reagents is of crucial importance. Because of that, one of the most important parameters aecting the transesterication reaction is the mixing eCorresponding author. Tel.: +40 21 316 7900; fax: +40 21 312 1601. E-mail addresses: mvinator@cco.ro, vinatorum@yahoo.com (M. Vinatoru). 1350-4177/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ultsonch.2006.09.014
*

ciency [10]. Our previous work regarding the continuous transesterication of vegetable oils under ultrasonic irradiation proved that ultrasounds could successfully replace the classical mixing-heating conditions [1114]. Ultrasonic irradiation is employed in a variety of industrial processes [15], but only a few examples of the application of sonochemistry at industrial scale were reported [16]. This paper presents the study of a possible ultrasonic continuous ow reactor able to act upon transesterication reaction. The eects of some features of the system such as the reactors volume and the residence time on the oils conversion to fatty acids methyl esters are discussed. The aim of present work is to investigate if ultrasounds could replace classical stirring and to provide an insight on a possible applicable technology in an attempt to move the use of ultrasounds towards other possible industrial applications. 2. Method 2.1. Reagents and materials Rened, bleached and deodorized (RBD) palm oil and commercial edible (CO) oil were purchased from Nisshin

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Ollio Co. (Tokyo, Japan). The oils had the following fatty acids composition (%) [17]: Fatty acid Lauric acid Myristic acid Palmitic acid Stearic acid Oleic acid Linoleic acid Linolenic acid Arachidic acid Gadoleic acid Palm oil 0.49 1.05 43.99 3.74 39.43 11.01 0 0.29 0 Commercial edible oil 0 0 5.51 2.50 32.88 52.52 5.86 0.30 0.44
Scheme 1. Setup of the ultrasonic continuous transesterication of vegetable oil.

The methanol employed in the reactions purchased from Wako Chemicals had more than 99.8% purity and was used as received. Potassium hydroxide (>95%) was purchased from Soda Nikka Co. Ltd. (Tokyo, Japan). The standards for fatty acid methyl esters and glycerides were obtained from SigmaAldrich Japan K.K. Tokyo, Japan. 2.2. Experimental procedure The sketch of the experimental setup is presented in the Scheme 1. The installation consisted of two reservoirs for the feedstock, an ultrasonic reactor, designed and built at Osaka Prefecture University, pumps for oil and methanolcatalyst solution and a separatory device. The sonochemical reaction chamber consisted of two glass cylinders giving two dierent reactor volumes. One reactor had the working volume of approximately 2.62 L. The other one had approximately 6.35 L. A pushpull ultrasonic transducer (Crest PP 05.45.255) having a frequency of 45 kHz and a total power of 600 W provided the ultrasonic irradiation. The reactions mixture temperature was 3840 C. The excess heat was dissipated by circulating cold water through the cooling jacket. For all experiments, the ultrasonic power supply was set to deliver 100% of the total power. The combined ow rate of pumps was established such that the residence time (RT) of the reaction mixture in the reactor equals to 10, 20 or 30 min. For each experiment, the reactor was initially completely lled up by pumping oil and methanol in a given ratio. The ultrasounds were o during the loading of the reactor. The pumps were stopped and afterwards the ultrasonic irradiation was started. The reaction was performed in a batch mode for a preset time equal to the RT. After that the feed pumps were re-started. This point was considered time zero of the reaction. The system was operated continuously without stopping the pumps or the ultrasonic irradiation for a time equal to twelve volume replacements. One volume replacement was equal to the reaction output in the established RT. For example, in the case of the small reactor, one volume replacement was 2.62 L. The total output of the small reactor, after 12 volume replacements was 31.44 L, while for the big reactor

the total output was 76.20 L, respectively, regardless the RT. The steady state was assumed to be after six volume replacements. This would allow the system to completely ush out the material from the starting runs and come to steady state conditions. At this point four run samples were collected at two volumes replacement. The 6, 8, 10 and 12 volume replacements were counted for constant ow (this ow assuring that in the established RT we had 2.62 L owing through the reactor) measured by the pumping time. 2.3. Analysis Aliquots (1 ml) were taken from the outlet at each two volumes replacement and left to stand for 2 h for products separation. An accurate amount of about 100 mg from the upper layer was diluted in the mobile phase to a concentration of 3% (w/w) and analyzed for the concentration of triglycerides, diglycerides, monoglycerides, and fatty acid methyl esters by reversed phase chromatography. The composition of the transesterication reaction products was determined by HPLC using a Shimadzu Chromatograph, consisting of a Model LC-10A HPLC pump and a Model RID 10A refractive index detector. The LC column was a Cadenza CD-C18 polymer-based column, 25 cm 3.0 mm with 4 lm diameter particle size silica. In all cases, the mobile phase was an acetone/acetonitrile mixture, 70:30 v/v, with a ow rate of 0.4 ml/min and a loop of 20 ll. By using standard grade reagents calibration curves were generated using as internal standard n-hexadecane. The molar concentrations of triglycerides and methyl esters (ME) were evaluated from the areas of relevant peaks, according to the following formula: C TG a ATG =AIS b C IS 100=M where a is the slope of calibration function; b is the intercept of calibration function; CTG is the weight percentage

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of triglycerides in the sample; ATG is the sum of peak area of individual triglycerides; AIS is the peak area of internal standard; CIS is the concentration of internal standard in the sample, weight; and M is weight of sample. The data presented are averages of three replicate determinations. 3. Results and discussion In order to explore the outcome at dierent molar ratios of alcohol to oil according to the reactor volume, our intention was to run complete experiments for 6/1 and 7.5/1 molar ratios methanol to oil, except the case of large reactor when for palm oil the 7.5/1 molar ratio was used. 3.1. Small reactor (2.62 L) In the case of a continuous process, the length of time the reagents remain in the reactor translates in the residence time. The results of continuous runs for CO carried out in the small size reactor under these conditions are presented in Fig. 1. As one can see in Fig. 1, in all cases the concentration of biodiesel exceeded 90%, and had a steady output. During the runs carried out at a 20 min RT and 10 min RT the concentration was almost the same with a minimal variability. The lower concentration of methyl esters at 30 min RT could be a consequence of the slow ow throughout reactor, due to the separation tendency of glycerol from esters; methanol, having higher solubility in glycerol, is going into the glycerol layer and is no longer available for emulsion formation. The induced asymmetric cavitational bubbles collapse at the oil alcohol boundary creates tiny drops of each liquid into other, leading to an enhanced mass transfer between the phases thus accelerating the reaction. The transesterication under ultrasonic irradiation is mainly inuenced by the superiority of the emulsion created by the collapse of cavitation bubbles in contrast to mechanical stirring.

Since the transesterication of oils with methanol is an equilibrium reaction, the use of a higher ratio of alcohol to oil should lead to a higher conversion. Under classical conditions, an excess in the molar ratio of the alcohol to oil resulted in an increase in the conversion [18]. We were interested to see if this applies in the case of continuous process under ultrasonic irradiation. Therefore, a set of experiments was carried out at a 7.5/1 molar ratio methanol to oil, at the same residence times as in the previous experiments. The results are presented in Fig. 2. As one can see in Fig. 2, the concentration of biodiesel in the product exceeded 95% even in the case of a long residence time. Thus, the presence of alcohol in higher amount, besides of its inuence in the equilibrium, leads to the generation of more cavitation bubbles and the conditions to form emulsion are better therefore the yield is higher. The characteristics of the emulsion could be inuenced by the energy input during emulsication, as well as by the amount of compounds engaged in the process. An increased amount of methanol determined a dierent composition and also a dierent distribution of droplets in the emulsion, leading to changes in the mass transfer between the phases. As a result, a higher conversion was attained when methanol/oil ratio is elevated. In order to investigate the inuence of the oil composition, palm oil was used for comparison. The results are presented in Figs. 3 and 4 and revealed a dierent behavior. Palm oil is partially solid at room temperature. In order to be fed in the reactor it had to be heated at 50 C to melt it. Once pumped into the reactor, palm oil enters in contact with the reaction mixture and partially solidies, thus disturbing the propagation of the ultrasonic eld. As soon as the reaction advances the formed methyl esters of fatty acids, which are extremely good solvents, dissolve the palm oil and for this reason the 3840 C temperature prevents the palm oil crystallization. Therefore, a longer residence time was necessary for the palm oil, than in the case of CO. Because of palm oil properties (solid at room temperature), the experiment carried out at a 6/1 molar ratio at

Fig. 1. Concentration of CO biodiesel for the small reactor at 6/1 molar ratio.

Fig. 2. Concentration of CO biodiesel for the small reactor at 7.5/1 molar ratio.

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Fig. 3. Concentration of palm oil biodiesel for the small reactor at 6/1 molar ratio.

Fig. 5. Concentration of CO biodiesel for the big reactor at 7.5/1 molar ratio.

Fig. 4. Concentration of palm oil biodiesel for the small reactor at 7.5/1 molar ratio.

10 min RT was impossible to be maintained under steady state conditions and no reliable data were obtained. For this reason in the Fig. 3 only the results of the other two residence times are presented. Even in these conditions the conversion decreased in time and steady state was impossible to achieve. In the case of 7.5/1 molar ratio alcohol to palm oil (Fig. 4), the excess amount of methanol led to formation of an increased number of cavitations and therefore of more emulsion centers and higher oil conversion. Consequently, the conversion of palm oil at 20 and 30 min RT was close to the CO oil and no crystallization occurs. However, when the residence time was 10 min a similar phenomenon as above was observed. Taken into account these results and because of the solid nature of palm oil, we can conclude that a residence time longer than 10 min and 7.5/1 molar ratio is necessary for its transesterication under continuous ultrasonic irradiation employed in this study. 3.2. Large reactor (6.35 L) This reactor was operated only at 7.5/1 molar ratio and at 30 and 20 min RT in order to have comparable data for palm and CO oils. The results obtained when the reaction

was performed at a 7.5/1 molar ratio for CO are presented in Fig. 5. When the size of the ultrasonic reactor was more than double (2.42 times bigger), the yield of biodiesel continuously decreased for a residence time of 30 min, reaching about 50% after about 6 h of reactor operation. This unexpected behavior could be the result of glycerol accumulation at the reactors bottom, trapping, in this way, more and more methanol into the glycerol layer. Therefore, methanol was no longer available in enough amounts to promote a constant conversion. This argument is consistently sustained by reducing the residence time to 20 min. At 20 min residence time, the yield was almost constant but did not exceed 90%. The transesterication of palm oil, performed in the bigger reactor did not maintain under steady state and had a very low conversion (Fig. 6). While the vegetable oil only propagates the ultrasonic waves, methanol is the cavitating liquid and the ultrasonic jets create small drops of methanol that penetrate the oil layer and form micro emulsions. By increasing the volume of the reactor, the ultrasounds power as well as bubbles density diminished thus, the contact area between the reac-

Fig. 6. Concentration of palm oil biodiesel for the big reactor at 7.5/1 molar ratio.

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tants was reduced. Consequently a low mass transfer between the reactants occurred, leading to a reduced biodiesel yield. In the case of palm oil the eect of higher reactors volume is amplied by the tendency of palm oil to crystallize thus disturbing the ultrasonic waves propagation throughout reaction mixture. However, the results of this study revealed that the setup of the transducer and consequently the design of the ultrasonic reactor, the physical properties of oil, residence time into the reactor as well as the alcohol/oil molar ration might play an important role in the ultrasonic manufacture of biodiesel. 4. Conclusion An ultrasonic reactor designed and build at Osaka Prefecture University was operated for continuously transesterication of vegetable oils. Ultrasonic irradiation proved suitable for large-scale processing of vegetable oils since relatively simple devices can be used to perform the reaction. The highest conversion was achieved when short residence time was employed. One advantage of ultrasonic continuous manufacture of biodiesel is a small reactor and the shorter reaction time. For a residence time of 20 min the small reactor could process around 7.8 L per hour while the larger one around 19 L. A better design of ultrasonic reactors for this type of process might lead to a more ecient mixing; the time of reaction could be shorter, thus substantially reducing the production costs. Acknowledgements The Romanian authors are grateful to ReEnergy LLC, Texas, USA for the nancial support in attending the

10th Meeting of European Society of Sonochemistry, 48 June, Hamburg, Germany 2006, where this paper was presented. References
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