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Ultrasonics Sonochemistry 16 (2009) 345350

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Ultrasound assisted synthesis of isopropyl esters from palm fatty acid distillate
Vishwanath G. Deshmane, Parag R. Gogate, Aniruddha B. Pandit *
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai-40019, India

a r t i c l e

i n f o

a b s t r a c t
Esterication is one of the most preferred synthesis routes for organic esters which are most frequently used as plasticizers, solvents and perfumery and avour chemicals. The present work deals with acid catalyzed synthesis of isopropyl esters from palm fatty acid distillate (PFAD) in the presence of ultrasonic irradiations operating at 25 kHz frequency and 1 kW of supplied power. Effect of different operating parameters such as molar ratio of reactants, catalyst quantity and operating temperature has been studied with an aim of optimization. It has been observed that ultrasound enhances the rate of reaction and the extent of equilibrium conversion. The optimum parameters for this process have been found to be 1:5 molar ratio of PFAD to isopropanol, catalyst concentration of 5% of PFAD and 60 C reaction temperature. Maximum conversion levels of about 80% have been obtained in 6 h of reaction time under these optimized conditions. Analysis of the kinetic data indicates that the reaction follows rst order reversible path. 2008 Elsevier B.V. All rights reserved.

Article history: Received 24 June 2008 Received in revised form 10 September 2008 Accepted 16 September 2008 Available online 26 September 2008 Keywords: Cavitation Isopropyl esters Palm fatty acid distillate Esterication Kinetics

1. Introduction Fatty acids alkyl esters such as isopropyl esters show an increasingly growing demand especially in Europe and the USA due to their numerous applications in cosmetic, pharmaceutical and food industries [1]. These also have considerable demand as biolubricants for high precision machinery and as biosolvents. In fact, in recent years, concern over the potential impact of petroleum-based solvents on the environment has created an opportunity to promote environmentally acceptable alternatives and biosolvents have been developed as one type of environment friendly product [2]. Several synthesis routes have been reported for the production of fatty acid esters ranging from extraction from natural sources to esterication in the presence of variety of catalysts and traditionally esterication is the most preferred route of synthesis [36]. Nowadays, new synthesis routes, either based on the use of cheaper raw materials or modications with an aim of process intensication such that the synthesis is much quicker, are being developed to produce esters in large quantities and at lower costs of production [710]. Use of cavitational reactors can favour the reaction chemistry and propagation by way of enhanced mass transfer and mixing between the phases and also can lower the requirement of the severity of the operating conditions in terms of temperature and pressure [11]. Cavitational reactors mainly rely on the phenomena of cavitation, which is generally described as the generation, subsequent growth and collapse of the cavities releasing large magni* Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614. E-mail address: abp@udct.org (A.B. Pandit). 1350-4177/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.ultsonch.2008.09.004

tudes of energy over a very small location resulting in very high energy densities [12]. Indeed, there have been some earlier illustrations referring to the use of cavitational reactors for esterication reactions [13,14] but mainly has been on the basis of use of pure vegetable oils and methanol for the synthesis of biodiesel. The costs associated with the use of pure vegetable oils for synthesis are exorbitant these days and hence there is a need always to look for alternative cheaper starting materials, especially for the reactions based on the use of cavitational reactors. A recent study [15] by our group reported the use of fatty acid odour cut as an alternative cheaper starting material for the synthesis of biodiesel in the presence of concentrated sulfuric acid as the catalyst. The present work evaluates the application of cavitational reactors for the synthesis of isopropyl esters, which seems to be quite novel approach as there has been no such earlier investigations to the best of our knowledge. The selected synthesis route is based on the esterication reaction between isopropyl alcohol (IPA) and palm fatty acid distillate (PFAD) in the presence of sulfuric acid as a catalyst (acid catalyst gives lower rates as compared to alkaline catalyst but in the present system alkaline catalysts cannot be used as this results in soap formation). The system has been deliberately chosen as all the earlier research in this area has considered the use of methanol or ethanol and pure raw materials for synthesis. PFAD is generally produced as a side product during the rening of palm oil and has a comparatively lower value as compared to the palm oil. Overall, the novelty of the present work lies in terms of new data for synthesis of isopropyl esters using ultrasonic irradiations based on the usage of a cheaper raw material. Effect of various parameters such as molar ratio of IPA to PFAD, presence and absence of the catalyst, concentration of catalyst,

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operating temperature and position of reactor with respect to radiating ultrasonic horn on the rate of reaction as well as equilibrium conversion have been investigated. 2. Materials and methods 2.1. Reaction scheme The reaction considered for the present study is the esterication of distilled palm oil fatty acid distillate (PFAD) with isopropyl alcohol under acid catalyzed condition to produce isopropyl esters. The reaction can be schematically depicted as follows:

CH3
98 % H2SO4

R1-COOH

+ CH3-CH-CH3 OH

R1-COO-CH CH3 IP- esters

+ H2O

Fatty acid

Isopropanol

This reaction is reversible endothermic reaction. To shift the equilibrium of the reaction towards the desired isopropyl esters, IPA has to be used in excess or water formed during the reaction needs to be continuously removed. In the present work, excess IPA has been used as a desired mode for the reaction to be taken to completion (IPA concentration has been selected as 39 times of the PFAD concentration). 2.2. Materials Palm fatty acid distillate was obtained from Godrej Ind. Ltd. (Mumbai, India). Analysis of the PFAD indicated the different components as palmitic acid (46.81%), oleic acid (35.31), stearic acid (4.72%), linoleic acid (8.38) and others (4.76%). IPA and sulfuric acid (98%) were procured from Merck (India) Ltd., Mumbai, whereas sodium hydroxide was procured from S.D. Fine-Chem Pvt. Ltd., Mumbai, India. All the chemicals were used as procured. 2.3. Experimental setup

an operating frequency of 25 kHz and a maximum rated power output of 1 kW. The ultrasonic transducer (surface area of 282.2 cm2) is tted at the bottom of the bath horizontally along the length of bath. The advantage of using such a system is that if offers much larger effective cavitational area as compared to a conventional immersion-based axial transducers and hence results in uniform cavitational activity distribution in the ultrasonic bath. The energy to this transducer was provided by a generator which is a separate unit. A schematic of the complete experimental assembly has been given Fig. 1. Calorimetric studies [16] were undertaken to estimate the actual power dissipated into the system. In this method, measured quantity of water is lled in ultrasonic bath and irradiated for a xed duration of time (10 min in the present case). The rise in temperature of the water is monitored with time to obtain the actual energy being dissipated into the water. It has been observed that the energy efciency is 21%, indicating that the actual available power for cavitational events was around 210 W. The observed intensity of irradiation, which is dened as actual power dissipated per unit transducer area, of the present ultrasonic system is thus equal to 0.74 W/cm2. 2.4. Experimental procedure The reactions were carried out in a three neck round bottom ask of 250 ml capacity. Condenser was mounted on it to provide the reux of the evaporating IPA. Initially a known quantity of PFAD was taken and melted under agitation separately. This molten PFAD was then charged to the reactor containing measured quantity of isopropyl alcohol with constant stirring. A known quantity of 98% sulfuric acid was added to the reaction mixture as a catalyst. Ultrasonic irradiations were started and samples were taken out at certain time intervals. The samples were titrated with 0.1 N NaOH solution to determine the amount of unconverted PFAD in terms of its acid value. The reactions were carried out till attainment of equilibrium conditions (no further reduction in the acid value). 3. Results and discussion

The experimental setup consists of an ultrasonic bath equipped with a transducer having longitudinal vibrations, procured from Roop Telesonic Pvt. Ltd., Mumbai, India. The ultrasonic unit has

We now discuss the effect of different operating conditions on the extent of equilibrium conversion and the rate of reaction. Ini-

Fig. 1. Schematic of the experimental setup used for ultrasound assisted esterication reaction.

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tially, quantication of the role of ultrasonic irradiations in intensifying the synthesis process was carried out by experiments in the presence and absence of ultrasound. 3.1. Effect of presence of ultrasound To demonstrate the effect of the presence of ultrasound, two experiments were carried out where in one case only ultrasound was used and in other case only agitation was used with all other reaction parameters viz. operating temperature (50 C), catalyst concentration (5% of PFAD) and reactants mole ratio (PFAD:IPA = 1:5) being kept constant. The obtained results have been depicted in Fig. 2. It has been observed that use of ultrasound enhances the limiting equilibrium conversion from about 65% in 7 h to about 75% in 6 h of reaction time. Thus, the use of ultrasonic irradiations is in both enhancing the rate of reaction as well as in shifting the equilibrium and resulting in higher product yields. Ultrasound generated cavitation results in conditions of intense turbulence and micro-scale liquid circulation currents which help in uniform mixing at micro-level and hence in the elimination of the mass transfer resistances [17]. It should also be noted that the observed effects are not so signicant in the present work as compared to the earlier work involving the reaction of fatty acid

cut with methanol [15] possibly attributed to lower degree of heterogeneity in the present case which marginally nullies the mass transfer resistances. Palm fatty acid distillate has much higher solubility in isopropanol as compared lower alcohols and hence results in lower mass transfer resistances. Since the effect of ultrasonic irradiations is mainly to eliminate the mass transfer resistances, the extent of intensication obtained in the case of isopropyl esters would be lower as compared to that obtained for the case where methanol or ethanol is used as a raw material. Experiments were also carried out to study the effect of reactor position with respect to the ultrasonic transducers. Two different positions of the reactor were used in same horizontal plane, i.e., at a xed perpendicular distance away from the transducer. The rst location was right at the center of the transducer length whereas the second location was at the end of the transducer. The obtained results for these sets of experimental investigations have been shown in Fig. 3. It can be easily seen that there is not much variation in the reaction progress with the change in the reactor position, which can be attributed to the uniformity in the ultrasonic pressure eld in this reactor. Earlier mapping investigations with the use of hydrophone for measuring the cavitational activity in the sonochemical reactor also conrmed this hypothesis [18] of uniform pressure and the cavitational eld. 3.2. Effect of molar ratio

80 70 60 Conversion (%) 50 40 30 Without Ultrasound 20 10 0 0 100 200 300 400 500 Time (min)
Fig. 2. Effect of the presence of ultrasound on the rate of esterication reaction.

With Ultrasound

The effect of molar ratio on the rate of reaction was investigated at four different molar ratios of PFAD to IPA viz. 1:3, 1:5, 1:7 and 1:9 with constant reaction temperature (50 C), Catalyst concentration (5% of PFAD) and reactor position with respect to ultrasonic transducer. As explained earlier, since alcohol has to be used in excess as compared to fatty acids, an operating ratio in the range 1:3 1:9 has been selected. The results have been shown in Fig. 4. One can easily observe from the gure that an initial increase in the mole ratio of the reactants from 1:3 to 1:5 signicantly increases the extent of equilibrium conversion but beyond this optimum mole ratio of 1:5, only marginal improvement in the rate of reaction and equilibrium conversion is observed. Kelkar et al. [15] have also reported similar observations for the esterication reaction of fatty acid odour cut and methanol. Excess alcohol in the system in the system contributes to higher cavitational intensity resulting into benecial effects as well as reduces the equilibrium limitation due to a larger excess of one of the reactants and due to its ability to dissolve the water of esterication. It should be also noted here that dependency of the rate of reaction on the mole ratio is less signicant in the present case as compared to the case of reaction between fatty acid cut and methanol [15], which can be attributed to

100 90 80
100 90 80

Conversion (%)

70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 Reactor at Centre Reactor at end

Conversion (%)

70 60 50 40 30 20 10 0 1:5 1:7 1:9 1:3

50

100

150

200

250

300

350

400

450

Time (min)
Fig. 3. Effect of reactor position on the rate of esterication reaction.

Time (min)
Fig. 4. Effect of molar ratio on the rate of esterication reaction.

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Conversion (%)

the higher solubility of PFAD in isopropyl alcohol and homogeneous nature of the resultant system. In the case of methanol, two different layers are formed during the progress of the reaction which ensures easy removal of water of reactions into the aqueous layer while the reaction usually occurs at the emulsion interface of the droplets formed in the reaction mixture [13]. Stavarache et al. [14] have also reported similar observations of lower yields of propyl esters as compared to methyl esters in the ultrasound assisted synthesis of esters of vegetable oils. 3.3. Effect of catalyst concentration The catalyst used in the current work was 98% sulfuric acid. Initially, preliminary experiments were carried out to check the necessity of the catalyst for ultrasound assisted synthesis process. However, it has been observed that no reaction is possible without the presence of catalyst clearly conrming the fact that cavitation phenomena does not change the reaction chemistry but only intensies the process by altering the physical processes, i.e., ensuring uniform mixing and mass transfer among different phases. Effect of catalyst concentration was investigated at four different concentrations viz. 1%, 3%, 5% and 7% (percent by weight of PFAD) of catalyst loading with constant reaction temperature (50 C), and molar ratio 1:5 (PFAD:IPA). The effect of catalyst concentration on the rate of reaction has been shown in Fig. 5. It can be seen from the gure that increase in rate of reaction is signicant for increase in the catalyst concentration from 1% to 3% as compared to further increase in the catalyst concentration from 3% to 5%. Also, an increase in the catalyst concentration beyond 5%, does not result in any further increase in rate of reaction and equilibrium conversion. Kelkar et al. [15] and Wen et al. [19] have reported similar effects of catalyst concentration on the ultrasound assisted esterication reactions. 3.4. Effect of reaction temperature The effect of temperature on the rate of reaction and equilibrium conversion was also studied by carrying out the reaction at four different temperatures over the range of 3060 C. The molar ratio PFAD to IPA was kept constant at 1:5 and the catalyst concentration was kept at 5% by weight of PFAD used. The results for the reactions at different temperatures have been given in Fig. 6. As seen from the gure, the reaction is observed to be very sensitive to the operating temperature. The rate of reaction as well as the equilibrium conversion rapidly increases with an increase in the temperature from 30 to 50 C but for an increase in temperature from 50 to 60 C the equilibrium conversion seems to be margin-

100 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400


30 C 40 C 50 C 60 C

Time (min)
Fig. 6. Effect of reaction temperature on the rate of esterication reaction.

ally affected, though it is reached much faster (6 h is the required time at 50 C as compared to only 4 h at 60 C). Further higher temperatures (>60 C) could not be evaluated in the present work due to limitations of the experimental system but based on the trends it is not expected to yield a signicant increase in the equilibrium conversions. Gronroos et al. [20] have reported similar effects of temperature in the ultrasound assisted esterication reactions whereas Bart et al. [21] have reported similar increase for the esterication of succinic anhydride with methanol by homogeneous catalysis. Yadav and Kulkarni [22] and Bouaid et al. [23] have also reported benecial effects of operating at higher reaction temperatures for the synthesis of isopropyl esters. 3.5. Kinetic modeling An attempt was made to develop a kinetic model for the esterication reaction as there is absolutely no information on the kinetic data for ultrasound assisted synthesis of isopropyl esters. The esterication reaction between PFAD and IPA is a reversible reaction and in the presence of sulfuric acid as a catalyst, takes place entirely under homogeneous condition. Analysis of the reaction data indicates that the reaction is rst order in forward direction and also rst order in backward direction. For the forward direction, IPA is taken in excess and hence the reaction would mainly depend on the concentration of fatty acid and follows a rst order behavior with respect to fatty acid concentration. In the case of backward reaction, as both ester and water of reaction affects the rate of reaction, there is a dependency of the rate on concentration of both ester and water. Since equi-molar quantities of water and ester are formed in the reaction, which are equally soluble in isopropyl alcohol, the overall dependency can also be considered as rst order. The overall rate of reaction can be expressed as follows:

100 90 80
1% 3% 5% 7%

Conversion (%)

70 60 50 40 30 20 10 0 0 50

  dFA k1 FA k2 E0:5 W0:5 dt

where (FA) is the concentration of PFAD, (E) is concentration of esters, (W) is concentration of water, k1 is rst order rate constant for forward reaction and k2 is the rst order rate constant for backward reaction. Since the molar concentration of ester and water are the same, the rate expression can be rewritten as
100 150 200 250 Time (min) 300 350 400 450

  dFA k1 FA k2 E dt

Fig. 5. Effect of catalyst concentration on the rate of esterication reaction.

In terms of conversion, the rate equation can be expressed as follows:

V.G. Deshmane et al. / Ultrasonics Sonochemistry 16 (2009) 345350

349

1 0.9 0.8 Conversion (X) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 50 100 150 200 250 Time (min) 300 350 400
E-60 C E-50 C E-40 C E-30 C M-60 C M-50 C M- 40 C M-30 C

Table 3 Kinetic parameters for reactions at different temperature S. No. 1 2 3 4 Temperature (C) 30 40 50 60 k1 105 (s1) 4.3 7.4 15.7 19.8 k2 105 (s1) 3.8 3.5 5 5.2 Equilibrium constant (K = k1/k2) 1.1 2.1 3.2 3.8

2.9E-03 -8.2 -8.4 -8.6 -8.8 ln (rate constant) -9 -9.2 -9.4 -9.6 -9.8 -10 -10.2

3.0E-03

3.1E-03

3.2E-03

3.3E-03

3.4E-03

Fig. 7. Fitting of experimental data with estimated data (sample set at varying reaction temperature).

  dX k1 1 X k2 X dt
where X is the fractional conversion of PFAD. The kinetic parameters of this reaction under different conditions have been estimated by using Matlab solver. The experimental results for sets of varying reaction temperature with all the remaining parameters being constant and results obtained from the simulation for the kinetic analysis have been compared in Fig. 7. It can be seen from the gure that a fairly good agreement between the experimental conversion data and that obtained using the kinetic rate equations exists. Similar agreement was also observed for reaction sets with varying mole ratio of the reactants and varying catalyst concentration. Using the values of the individual rate constants for forward and backward reactions (k1 and k2), the equilibrium constants were determined and have been given in Tables 13 for all the reaction sets investigated in the present work. The obtained values of the kinetic parameters explain the variation of the different operating parameters as discussed in details in the earlier discussion. It should be noted here that generated model in the present work is only indicative and preliminary for ultrasound assisted esterication reactions and by no means a generalized one. A more rigorous model can be developed, if the individual concentrations of propyl ester, i.e., that of palmitic, oleic, stearic acids are known as function of time.

(1/Temperature)
Fig. 8. Arrhenius plot for obtaining the Activation energy for the esterication reaction.

Since the effect of operating temperature was signicant as compared to other operating parameters such as the mole ratio and catalyst concentration, it was thought desirable to obtain more kinetic details in terms of the activation energy for the reaction. Fig. 8 shows the variation of the rate constant for the forward desired reaction with temperature plotted in terms of an Arrhenius plot. The value of the activation energy for the esterication reaction has been obtained to be equal to 1.07 104 Kcal/mol. Yadav and Kulkarni [22] have reported that the activation energy for synthesis of isopropyl lactate using stirred conditions is 2 104 Kcal/ mol though in the presence of ion exchange resin catalysts. Lower values of the activation energy in the presence of ultrasound also explain the utility of cavitation phenomena in intensication of the esterication reactions. 4. Conclusions

Table 1 Kinetic parameters for reactions at different molar ratios S. No. 1 2 3 4 Molar ratio (PFAD/ IPA) 1:3 1:5 1:7 1:9 k1 105 (s1) 14.2 15.7 11.8 11.7 k2 105 (s1) 5.5 5.1 3.1 2.5 Equilibrium constant (K = k1/k2) 2.6 3.1 3.8 4.7

Table 2 Kinetic parameters for reactions at different catalyst concentrations S. No. 1 2 3 4 Catalyst concentrations (% of PFAD) 1 3 5 7 k1 105 (s1) 3 10.8 15.7 17.3 k2 105 (s1) 2.1 4.2 5 5.35 Equilibrium constant (K = k1/k2) 1.4 2.6 3.2 3.2

The present work has enabled us to establish a relatively novel synthesis route for isopropyl esters from palm fatty acid distillate, a comparatively cheaper raw material, as compared to the vegetable oils. Use of cavitating conditions helps in increasing the equilibrium conversions and also enhancing the rates of reaction. The effect however is not so signicant as compared to other esterication reactions involving methanol due to a nearly homogeneous nature of the reaction mixture which reduces the interphase mass transfer resistance. The optimum operating parameters for the present work were observed to be 1:5 mol ratio of PFAD to IPA, 5% of catalyst concentration and 60 C as the reaction temperature. A kinetic model has been developed, which has been a missing link in ultrasound assisted esterication reactions and the obtained values of the rate constants suitably explained the effect of the various operating parameters.

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V.G. Deshmane et al. / Ultrasonics Sonochemistry 16 (2009) 345350 [12] T.J. Mason, Practical Sonochemistry: Users Guide in Chemistry and Chemical Engineering, Ellis Horwood Series in Organic Chemistry, Chichester, UK, 1992. [13] C. Stavarache, M. Vinatoru, Y. Maeda, Ultrason. Sonochem. 13 (2006) 401. [14] C. Stavarache, M. Vinatoru, Y. Maeda, Ultrason. Sonochem. 12 (2005) 367. [15] M.A. Kelkar, P.R. Gogate, A.B. Pandit, Ultrason. Sonochem. 15 (2008) 188194. [16] P.R. Gogate, I.Z. Shirgaonkar, M. Sivakumar, P. Senthilkumar, N.P. Vichare, A.B. Pandit, AIChE J. 47 (2001) 25262538. [17] A.B. Pandit, V.S. Moholkar, Chem. Eng. Prog. 92 (1996) 5767. [18] A. Kumar, P.R. Gogate, A.B. Pandit, Ultrason. Sonochem. 14 (2007) 538544. [19] B. Wen, W. Eli, Q. Xue, X. Dong, W. Liu, Ultrason. Sonochem. 14 (2007) 213 218. [20] A. Gronroos, N. Aittokallio, E. Kolehmainen, Ultrason. Sonochem. 11 (2004) 161165. [21] H.J. Bart, J. Reidetschlager, K. Schatka, A. Lehmann, Int. J. Chem. Kinet. 26 (1994) 10131021. [22] G.D. Yadav, H.B. Kulkarni, React. Funct. Polym. 44 (2000) 153165. [23] A. Bouaid, J. Aparicio, M. Martnez, J. Aracil, Enz. Microbiol. Technol. 41 (2007) 533538.

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] R.D. Whitby, Lipid Technol. 16 (2004) 125130. J.B.M. Rattray, J. Am. Oil Chem. Soc. 61 (1984) 7011712. F. Ma, M.A. Hanna, Biores. Technol. 70 (1999) 115. L.C. Meher, D. Vidya Sagar, S.N. Naik, Renew. Sust. Energy Rev. 10 (2006) 248 268. M.A. Ogliaruso, J.F. Wolfe, Synthesis of Carboxylic Acids, Esters and their Derivatives, Wiley, New York, 1991. G.D. Yadav, P.H. Mehta, Ind. Eng. Chem. Res. 33 (1994) 21982208. R. Alcantara, J. Amores, L. Canoira, E. Fidalgo, M.J. Franco, A. Navarro, Biomass Bioenergy 18 (2000) 515. S.V. Ranganathan, S.L. Narasimhan, K. Muthukumar, Biores. Technol. 99 (2008) 39753981. G. Madras, C. Kolluru, R. Kumar, Fuel 83 (2004) 20292033. J. Hernando, P. Leton, M.P. Matia, J.L. Novella, J. Alvarez-Builla, Fuel 86 (2007) 16411644. P.R. Gogate, Chem. Eng. Process. 47 (2008) 515527.