N. Jaya et al.

/ International Journal of Engineering Science and Technology (IJEST)

KINETIC MODELING OF TRANSESTERFICATION REACTION FOR BIODIESEL PRODUCTION USING HETEROGENEOUS CATALYST
N. JAYA
Department of Petrochemical Technology, Anna University of Technology, Tiruchirappalli, Tiruchirappalli, Tamil Nadu 620 024, India

K. ETHIRAJULU
Director , Krishnasamy College of Engineering and Technology, Cuddalore, Tamil Nadu 607 109, India Abstract : Biodiesel derived from renewable plant sources is monoalkyl esters of long chain fatty acids which fall in the carbon range of C12-C22. It has similar properties as mineral diesel. Various processes exist to convert vegetable oils into biodiesel. Transesterification of such vegetable oils using alcohol in the catalytic environment is most commonly used method for producing biodiesel. The equilibrium conversion of triglycerides is affected by various factors namely feed Quality (like free fatty acid content, water content etc.), type of alcohol used, molar ratio of alcohol to triglycerides, type of catalyst, amount of catalyst, reaction temperature, reaction time and stirring rates. The present work reports on the characterization of cotton seed oil and production of biodiesel. This study also reports on the optimal operating parameter for cotton seed oil in batch reactor. The main thrust of present work was to study the kinetics, modeling and simulation of anionic ion exchange resin catalyzed transesterification of cotton seed oil. Experiments were carried out in batch reactor to generate kinetic data and a kinetic model was developed. The effect of temperature, catalyst concentration and molar ratio of methanol to triglycerides and stirring rates were investigated. A few fuel properties were also measured for biodiesel to observe its competitiveness with conventional diesel fuel. The equilibrium conversions of triglycerides were observed to be in the range of 85%. It was also observed that higher conversion was achieved at 6:1 molar ratio of ethanol to oil, 2 wt.% of anionic resin catalyst ,temperature at 338 K, reaction time of 180 minutes with stirring speed 10 Hz. Model parameters such as order, activation energy and rate constants were calculated, the overall activation energy was also estimated. The rate constants were found to increase with an increase in temperature and catalyst concentration. Various simulations were also carried out at different conditions. Effects of varying parameters were studied in simulations. This simulation leads to a better understanding of the influence of the interactions between the reaction parameters and also helps to improve the efficiency of the transesterification process. Keywords: Biodiesel; Transesterification; Cotton seed oil; Anionic ion exchange resin; Simulation. 1. Introduction Biodiesel is a promising alternative or extender to conventional petroleum based diesel fuel. Biodiesel has a number of advantages it is derived from a renewable domestic resource (Vegetable oil), reduces carbon dioxide emissions by78%, when compared to diesel fuel on lifecycle basis, and is nontoxic and biodegradable, making it more environmentally benign fuel[4]. Generally biodiesel is produced via transesterification reaction between vegetable oil (composed of complex mixture of triglycerides) and lower molecular weight alcohol such as methanol. The reaction is C57H10O6 +3CH3OH 3C19H36O2+C3H8O3,. (1) Aspen plus process modeling software is used to model biodiesel production process from cottonseed oil. Aspen plus was used because of the thorough treatment of thermodynamic interactions and its status as a widely accepted process simulator[5] .Because most of the physical property data for many of the key components used in the simulation of biodiesel production are not available in the standard ASPEN-plus property databases, values from an in house database (INHSPCD) developed by National Renewable Energy Laboratory (NREL)[8].Computer Aided design and simulation gives the process engineer the ability to evaluate more design alternatives in more detail than possible hand calculations. The purpose of this work is top define the

ISSN : 0975-5462

Vol. 3 No. 4 April 2011

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N. Jaya et al. / International Journal of Engineering Science and Technology (IJEST)

heterogeneous acid catalysed process simulation and to perform detailed optimization ,as well as conduct sensitivity analyses on key process parameters such as reaction. 2. Experimental Methodology The major constituent of cottonseed oil are Triglycerides(60-70%) and the rest are di and monoglycerides.the main key factors during transesterification reaction are the percentage of free fatty acid and moisture,[9] because these two favor the side reactions like saponification and hydrolysis and lower the yield of methyl ester. 2.1. Process Modeling and Simulation ASPEN Plus version11 .1 was used to conduct the simulation. Plant capacity, unit block operating conditions, and chemical components (except the catalyst) were selected based on the previous heterogeneous acid catalyst (Styrene divinyl benzene copolymer) simulation [1]. For the present simulation styrene divinyl benzene was chosen as the catalyst, as it has been shown to effectively catalyze both the transesterification and esterification reactions by several authors[2],[3],[4], whereas the use of styrene divinylbenzene copolymer has only been demonstrated. Although the properties for triolein were available in the ASPEN data banks, different values for the boiling point and critical temperature were obtained from the literature [6] and used to Re-estimate the Antoines vapor pressure coefficients since initial estimates and results were unsatisfactory. The NRTL model was selected as the thermodynamic model. Since no kinetic data were available for the styrene divinyl benzene copolymer reaction, the reactor was modeled as a stoichiometric reactor representing a packed bed reactor, eliminating the catalyst removal step[4]. The conversion was set at 85%. It was assumed that no side reactions involving glycerol occurred, since there had been no reports of such reactions in the literature. Details of the reactor conditions are outlined in Table 1. Catalyst characteristics such as density and porosity have not been included in the reaction scheme since they have not been reported in the literature and are likely to change with each method of synthesis. Additionally, since the reactor is modelled as a batch reactor, including such parameters would not have affected the results 2.2. Process Design In the process vegetable oil was transesterified in the reactor, followed by downstream purification, which consisted of: methanol recovery by distillation; glycerol separation; and methyl-ester purification by distillation. Table 1 gives details for the unit operations in the process. Table 2 presents the feed and product material flow details for the process. Multi-stage distillation was used to recover the excess methanol, as well as in the final purification of bio diesel. Distillation columns were specified to meet or exceed the ASTM standard for biodiesel purity, i.e., 99.65 wt. %. Reflux ratio s for the columns was calculated by the unit operation blocks as a design variable. In order to achieve high methanol recovery, vacuum operation in the methyl-ester purification column was necessary to keep the temperature of the bottom stream low enough, as glycerol is subject to degradation at temperatures above 150C [9],[7], gravity separation was used to separate the biodiesel from the glycerol, and a satisfactory separation was achieved. While this particular separation has not been verified experimentally, Chiu et al. (2005) showed that methanol dissolves almost entirely in the glycerol phase of a methanol-glycerol-biodiesel mixture indicating that theoretically, a decanter is able to achieve high purity separation[6]. The final purity of the methyl-ester product was quantified by reporting the product stream composition, which was determined by thermodynamic calculations in ASPEN. Mono- and di-glycerides were neglected as reaction intermediates [10]. 3. Results and Discussion An ASPEN-Plus model was used to design the process and to estimate the corresponding results. Simulation results were generated for ten different conditions, consisting of seven temperatures (303,313, 323, 328, 333, 338, and 343 K). For each set of parameters, a corresponding mass and energy balance sheet was generated by the ASPEN-Plus software.

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3.1. Process Design Sensitivity analyses were conducted to determine the effect of reactor conversion. The methoxide species, which are thought to be the active species in transesterification reactions, are formed upon adsorption of methanol on the catalysts surface and the transesterification reaction becomes mass transfer-controlled. As the methanol/oil ratio increases, the driving force for methanol adsorption increases as well, thus favoring

Fig. 1. ASPEN-Plus process flow diagram for the production of biodiesel from cottonseed oil.

the transesterification reaction. In this work, the effects of the molar ratio of methanol to cottonseed oil in the range of 3-12 and the results shows that 6:1 molar ratio gives >80 % of conversion within 3 h as shown in Fig. 1. Higher molar ratio of alcohol to vegetable oil interferes with separation of glycerol because there is an increase in solubility. When glycerol remains in solution, it helps to drive the equilibrium back to the left, lowering the yield of esters.

Fig. 2. simulation results for molar ratio of 6:1

Fig .3. Effect of molar ratio of methanol to cottonseed oil on the biodiesel yield at 338 K with 1.5 wt % of cation resin catalyst.

The impact of reaction temperature of the transesterification reaction in the range of 303-343 K on the yield of biodiesel was examined as shown in Fig. 3. With increasing temperature, due to higher energy state of the molecules resulting more fruitful collision and higher solubility of reactants at elevated temperature, the reaction rate increases. At the reaction temperature of 338 K, an elevated yield of biodiesel was observed in cationic environment within 3 h. At higher reaction temperatures, there is a chance of loss of methanol and increase in darkness of the product. This also increases the production cost of biodiesel

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N. Jaya et al. / International Journal of Engineering Science and Technology (IJEST)

Fig 4: simulation results for reaction temperature of 338K Fig. 5: Effect of reaction temperature on the yield of biodiesel with 1.5 wt % of cation catalyst, 6:1 molar ratio and 10 Hz

4. Conclusion Now days, biodiesel is produced in great amount and its production continues to grow. The main technology used in the industrial production is based on the transesterification of refined oils with methanol using basic homogeneous catalysts. However, the problems related with this technology have stimulated research in the field of heterogeneous catalysis for biodiesel production. In view of these results; we found that when the heterogeneous catalyst was used in the transesterification of cottonseed oil with methanol to produce biodiesel, high production efficiency was obtained with mild reaction conditions. The biodiesel as high as 80 % was obtained with the molar ratio of methanol to cottonseed oil of 6:1, a catalyst amount of 1.5 wt %, a reaction temperature of 338 K, a stirring rate of 10 Hz and a reaction time of 3 h. We have also found that the activation energy of cation catalyzed transesterification of cottonseed oil is 22090.30 J/mol. The lower activation energy indicating that methanol biodiesel has better combustion properties. The reactions are completed under mild temperature and pressure conditions. This ion exchange catalyst can also be applied in other chemical reactions as solid acid catalysts. This can be easily recovered by simple filtration and reused several times with consistent activity. Simulation results variation is observed as 3% with experimental process. References
Eugena.L; Rudolph.V. (2008). Transesterification of vegetable oil to biodiesel over MgO-functionalized mesoporous catalyst, Energy & Fuels, 22, pp. 145-149. [2] Tanguy. F. D; Marie-Francoise. R; Guy B. M. (2006). Kinetics of heterogeneously MgO-catalyzed transesterification, Applied Catalysis, 61, pp. 35-45. [3] Kucek. K. T and et. Al.(2007).Ethanolysis of refined soybean oil assisted by sodium and potassium hydroxides, J. Am. Oil Chem. Soc., 84, pp. 385-392. [4] Shengping.W and et.al. (2004). Transesterification of dimethyl oxalate with phenol under SnO2/SiO2 catalysts, Ind. Eng. Chem. Res, 43, pp. 4027-4030. [5] F. Mingming, and Z. Pingbo, Activated carbon supported K2CO3 catalyst for transesterification of dimethyl carbonate with propyl alcohol, Energy & Fuels, vol. 21, pp. 633-635, 2008. [6] Pintoa. A. C. and et.al. (2005). Biodiesel: An overview, J. Braz. Chem. Soc, 16, pp. 1313-1330. [7] Lotero. B.J and et.al. (2006). The catalysis of biodiesel synthesis, Catalysis, 19, pp. 41-83. [8] Canakei. M; Sanli. H. (2008). Biodiesel production from various feedstocks and their effects on the fuel properties, J. Ind. Mocrobiol. Biotechnol, Bioenergy special issue. [9] Ma.H and et.al.(2008). Transesterification of rapeseed oil for synthesizing biodiesel by K/KOH/-Al2O3 a heterogeneous base catalyst,J. Am. Oil Chem. Soc., 85, pp. 263-270. [10] Jitputti.J and et.al.(2006). Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts, Chem. Eng. J, 116(1), pp. 61-66. [11] Simone.C.M and et.al. (2005). Transesterification of Brazilian vegetable oils with methanol over ion-exchange resins, J. Am. Oil Chem. Soc..82 (9),pp 661-665 [1]

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