American International Journal of Research in Science, Technology, Engineering & Mathematics

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ISSN (Print): 2328-3491, ISSN (Online): 2328-3580, ISSN (CD-ROM): 2328-3629 AIJRSTEM is a refereed, indexed, peer-reviewed, multidisciplinary and open access journal published by International Association of Scientific Innovation and Research (IASIR), USA
(An Association Unifying the Sciences, Engineering, and Applied Research)

Kinetic Study of Catalyzed and Uncatalyzed Esterification Reaction of Acetic acid with Methanol
M.B. Mandakea, S.V. Anekarb, S.M.Walkec Department of Chemical Engineering, Tataysaheb Kore Institute of Engineering and Technology, Waranangar, Kolhapur 416113, India. b Department of Chemical Engineering, Tataysaheb Kore Institute of Engineering and Technology, Waranangar, Kolhapur 416113, India. c Department of Chemical Engineering, Bharati Vidyapeeth college of Engineering, Navi Mumbai, India.
a

Abstract: The kinetics of esterification of acetic acid with methanol will be investigated extensively for homogenous and heterogeneous catalyzed reactions. The experiments will be carried out in a batch stirred reactor at different temperatures by using ion exchange resin as a catalyst. The concentration time profile will be observed for different sets of conditions. The effects of temperature, Catalyst loading and feed molar ratios on reaction kinetics will also be studied. The activation energy and equilibrium constants for this reaction will be determined experimentally at different temperatures. The temperature dependency of the constants appearing in the rate expression will also be determined. Key Words: Esterification, Kinetics, Heterogeneous, Catalyst, Methyl Acetate, Ion exchange resin. I. Introduction There is an increasing the inclination of chemical industries toward new processes that should meets requirement such as generation of nearly zero waste chemicals, less energy, and sufficient uses of product chemicals in various application. Hence the esterification is widely employed reaction in the organic process industry. The reaction is carried out between carboxylic acid and alcohol at with or without present of different acid catalyst under such specific conditions. Esters are used as solvents of paints, adhesives and organic media instead of aromatic compounds. Esterification reactions are extremely slow; it requires several days to attain the equilibrium in the absence of a catalyst. To accelerate the reaction rate, catalysts are always employed in liquid phase esterification. Despite the strong catalytic effect, the use of homogenous catalysts, such as Sulphuric acid and p-toluenesulphonic acid suffers from several draw-backs, such as the existence of side reactions, corrosion of the equipment and the need to deal with acidic wastes. Homogenous catalysts may also result in sulphur contamination of the final ester product. In this situation, the use of solid catalysts has received increasing attention in the past years. Many solid-acid catalysts have been used, such as iodine, zeolite-T membrane, ZSM5, HY zeolite, zeolite beta, acid treated clays, heteropolyacids, copper catalysts, sulphated oxides and zirconia. Ion exchange resins, however, are the most commonly used solid acid catalysts instead of liquid ones. The goal of this work was to study the esterification kinetics of acetic acid with methanol in the presence of catalyst and in the absence of catalyst. The effect of the reaction temperature, the initial molar ratio of the reactants, the catalyst loading and the stirrer speed on esterification kinetics were studied. CH3COOH + CH3OH CH3COOCH3+ H2O Most reactions catalyzed by ion exchange resins can be classified as either a quasihomogenous or a quasiheterogeneous. The kinetics of this model reaction catalyzed by Amberlyst-15 was described as a quasihomogenous and a quasiheterogeneous model. II. Experimental A. Chemical and catalysts All chemicals and catalysts were procured from firms of repute and used without further purification: Acetic acid (S.D. Fine Chemicals, Mumbai India), Methanol (Merck India), Amberlyst-15 (Rohm and Hass, USA). The physical properties of these resins are reported in Table 1. The macroporous resin was dried at 70 0C for 6 hrs in vacuum drier before use. In all the experiment, the dried catalyst was used. Table 2.1:- Properties of Amberlyst-15 ion exchange resin
Shape Average particlesize (mm) Internal surface area (m 2 /gm) Capacity (meq /gm) Cross-linking density (% DVB) Porosity (%) Max.operating temperature ( C) Beads 0.5 55 4.7 20-25 36 120

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B. Reaction Procedure The reaction was carried out in a 500 ml glass reactor of 7.5 cm I.D. equipped with four equally spaced full baffles and four- bladed turbine impeller. The reaction temperature was maintained by means of a thermostatic water bath in which the reaction assembly was immersed. Reactions were carried out in the presence and in the absence of Amberlyst-15 resin catalyst. The reaction mixtures were allowed to reach the desired temperature and the zero time sample was collected. Agitation speed was then commenced at sufficiently high speed measured with a tachometer. In most of the cases, alcohol was taken in far molar excess over acetic acid to drive the equilibrium away towards the ester formation. C. Analysis For kinetic measurements, samples were withdrawn periodically and analysed by instrumental methods. The product distribution in the sample was determined by Gas Chromatography (GC) on a CHEMITO 7610 gas chromatograph machine (Thermo Fisher Pvt. Ltd, India) equipped with Flame Ionisation Detector. A 3 m long stainless steel column of 0.3175 cm I.D., packed with OV-17 on chromosorb was used for the analysis. III. Results and discussion To shift the equilibrium towards the formation of the desired product, excess methanol was used in the reaction. The preliminary experiments were con ducted under otherwise similar conditions of reactant concentration (or mole ratio), catalyst loading, speed of agitation, and temperature except the type of catalyst. Kinetics for Uncatalyzed Reaction: A. Elimination of mass transfer resistance Preliminary experiments were carried out to evaluate the influence of the different mass transfer resistances. The batch (solid-liquid and solid-liquid-liquid) reactions were carried out over a wide range of speed of agitation 800-1200 RPM to study the external mass resistance. It was observed that beyond 1000 RPM there was no appreciable change in the rate of the reaction. Hence all the reactions were conducted at 1000 rpm to ensure that there is no resistance to mass transfer at any existing solid-liquid and liquid-liquid interface. B. Effect of temperature The study of the effect of the temperature is very important since it is useful to calculate the activation energy of the reaction. The effect of temperature was studied over a temperature range of 308 K to 328 K. The experiments were carried out at three different temperatures i.e. 308K, 318K and 328K with 1:3 molar ratios of acetic acid and methanol, and 1000 rpm speed for uncatalyzed reactions. Results obtained in the Fig.3.1 indicate that for the limiting component the rate of reaction and conversion are sensitive to a change in temperature. Fractional Conversion of Acetic acid increases with increase in temperature for uncatalyzed reactions.

0.12

B X(1:3,308k,1000rpm) C X(1:3,318k,1000rpm) D X(1:3,328k,1000rpm)

0.10

Frac. Conversion

0.08

0.06

0.04

0.02

0.00 0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 3.1: Effect of Temperature on Acetic Acid in Uncatalyzed reaction: AA: MeOH mole Ratio = 1:3, rpm=1000 C. Effect of mole ration of reactants For uncatalyzed reactions the experiments were conducted at different mole ratios like 1:1, 1:2, and 1:2 of acetic acid and methanol at 55 C, 1000 rpm speed. Results obtained in the Fig.3.2 shows the effect of mole ratio of alcohol to acetic acid on the reaction kinetics. As expected the rate and equilibrium conversion of the limiting

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reactant increase with increase in mole ratio. It was observed that fractional conversion of acetic acid goes up to high as 14% for the mole ratio of 1:3, 550C, and 1000 rpm for uncatalyzed reactions.

0.15

B X(308K,1:1,1000rpm) C X(318K,1:2,1000rpm) D X(328K,1:3,1000rpm)

Frac. Conversion

0.10

0.05

0.00 0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 3.2: Effect of Mole ratio on Acetic Acid in Uncatalyzed reaction: Temperature = 328 K, rpm=1000 Kinetics for Catalyzed Reaction D. Effect of presence of catalyst

The catalytic activity of the resin was first tested qualitatively through two experiments with different catalytic conditions. In the first one, a non-catalyzed reaction was conducted in a homogeneous liquid phase; in the second, the commercial resin Amberlyst-15 was used. Both the reactions are carried out at 55 C, 1:3 molar ratios of acetic acid and methanol at 1000 rpm speed of agitator. For the reaction with catalyst 10wt% of catalyst dried under vacuum for 8 hrs at 343 K was used. Esterification reaction can take place even in the absence of the catalyst due to the weak acidity of acetic acid itself. However, it was observed that the reaction is extremely slow.

B (With Catalyst) C (Without Catalyst)

0.5

Frac. Conversion

0.4

0.3

0.2

0.1

0.0 0 20 40 60 80 100 120 140 160 180 200

Time(min)

Figure 3.3: Effect of presence of catalyst: Temperature= 328 K, AA: MeOH mole ratio=1:3, rpm= 1000, catalyst loading=10WT% After about 3 hrs, when the catalyzed processes have already reached equilibrium, the conversion achieved in the non-catalyzed reaction was 14% while in catalyzed reaction it was 54%. E. Effect of Catalyst Loading The experiments were conducted with different catalyst loadings i.e. 2.5 wt%, 5 wt% and 10wt% at 55 C, 1:3 molar ratio of acetic acid and methanol and 1000 rpm speed. It was found that with increase in catalyst loading results in an increase in the rate of reaction and fractional conversion of acetic acid because of an increase in number of active sites, which again indicates that mass transfer resistances are absent and the reaction is only

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controlled by intrinsic kinetics. At higher catalyst loading the rate of mass transfer is excessively high and therefore there is no more increase in the rate.
B(2.5wt%,328K,1:3,1000 rpm) C(5wt%,328K,1:3,1000 rpm) D(10wt%,328K,1:3,1000 rpm)

0.60 0.55 0.50 0.45

Frac. Conversion

0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 3.4: Effect of catalyst loading on Acetic Acid: Temperature= 328 K, AA: MeOH mole ratio=1:3, rpm=1000 F. Effect of Temperature The effect of temperature was studied over a temperature range of 308 K to 328 K. The experiments were carried out at three different temperatures i.e. 308K, 318K and 328K with 1:3 molar ratios of acetic acid and methanol, 10 wt% catalysts, 1000 rpm speed. Results obtained in the Fig.3.5 indicate that the rate of reaction and conversion are sensitive to a change in temperature. It was seen that Conversion of limiting reactant increases with increase in temperature.
B X(308K,1:3,10Wt%,1000rpm) C X(318K,1:3,10Wt%,1000rpm) D X(328K,1:3,10Wt%,1000rpm)

0.6

0.5

Frac. Conversion

0.4

0.3

0.2

0.1

0.0 0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 3.5: Effect of Temperature on Acetic Acid: AA: MeOH mole ratio=1:3, rpm=1000, Catalyst loading= 10 wt% G. Effect of Mole Ratio The concentration of methanol has an influence on the reaction rate and on the concentration. The experiments were conducted at different mole ratios like 1:1, 1:3, and 1:5 of acetic acid and methanol at 55 C, 10 wt% catalysts, 1000 rpm speed. Results obtained in the Fig. 3.6 shows the effect of mole ratio of alcohol to acetic acid on the reaction kinetics. As expected the rate and equilibrium conversion of the limiting reactant increase with increase in mole ratio. It was observed that fractional conversion of acetic acid goes up to high as 54% for the mole ratio of 1:3, 550C, and 1000 rpm.

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0.60 0.55 0.50 0.45

B X(328K,1:1,10Wt%,1000rpm) C X(328K,1:2,10Wt%,1000rpm) D X(328K,1:3,10Wt%,1000rpm)

Frac. Conversion

0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 20 40 60 80 100 120 140 160 180 200

Time (min)

Figure 3.6: Effect of Mole ratio on Acetic Acid: Temperature= 328 K, rpm=1000, catalyst loading= 10 wt% 3.8 Reaction Kinetics Since the external mass transfer resistance and the intraparticle diffusional resistance were absent, the reaction was kinetically controlled. The catalyst used is a macroporous ion-exchange resin. This is because, in a macroporous resin, the pores are so large (>400 A0) that the reactants are able to diffuse into the pores and the products to diffuse out without any resistance. This is the so called pseudo homogeneous model. a. Kinetic model Esterification of Acetic acid with Methanol is given as
CH 3 COOH CH 3 OH CH 3 COOCH H 2O

(1)

Esterification reactions are known to be second- order reversible reactions. Therefore, for the bimolecular-type second order reactions. sA B (2) E W With the restrictions that C AO C BO and C EO CWO , the rate can be written as

rA

dC A dt

C AO

dX A dt

k1C A C B

k 2 C E CW

(3)

2 k1C AO (1 X A ) 2

k 2 (C AO X B ) 2

Where A, B, E, and W refer to Acetic Acid, Methanol, Methyl Acetate and Water, respectively. At the equilibrium, rA 0 . Hence, from the above equations, we find the fractional of A at the equilibrium conditions by

C Ee CWe C Ae C Be
k1 k2

2 X Ae

1 X Ae

(4)

And the equilibrium constant by

(5)

Combining the above three equations, in terms of the equilibrium conversion, we obtain
dX A dt k1C AO 1 XA
2

X Ae X Ae

2 2 XA

(6)

With conversions measured in terms of XAe, this may be indicated as a pseudo second-order reversible reaction which, on integration, gives X Ae 2 X Ae 1 X A 1 (7) ln 2k1 1 C BO t X Ae X A X Ae Temperature and Reaction Rate: We can examine the variation of the rate constant with temperature by an Arrhenius law relationship.

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k1

k10 exp

EA RT

(8)

This is conveniently determined by plotting lnk1 versus 1/T. b. Kinetics for Catalyzed Reaction The experimental data collected at temperatures of 308 K, 318K and 328K at molar ratios of acetic acid to methanol of 1:1 and at a stirring speed of 1000 rpm were used to plot the left-hand side (LHS) of Eq. (7) versus time to get a straight line passing through the origin, thus suggesting that the model developed is adequate to represent the system.
B X(308K) C X(318K) D X(328K)

LN((XAe-(2*XAe-1))/(XAe-XA)) v/s Time

LN((XAe-(2*XAe-1))/(XAe-XA))

2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 20 40 60 80 100 120 140 160

Time(min)

Figure 3.7: Typical kinetic plots for the effect of temperature on Catalyzed Reaction. Catalyst loading = 10wt%, speed of agitation = 1000 rpm, mole ratio of acetic acid to methanol = 1:1 The optimized values of the heterogeneous reaction rate constants are presented in Table 3.1 Table 3.1: Reaction rate constants for heterogeneous catalyzed esterification
Temp., K 308 318 328 K1 L.mol-1 .min-1 0.060013 0.081278 0.147012 K2 L.mol-1 .min-1 0.807277 0.901893 1.25339

c. Kinetics for Un-Catalyzed Reaction For the kinetic study of the uncatalyzed esterification reaction, the experiments are carried out at 308K, 318K, and 328K at molar ratios of acetic acid to methanol of 1:1 and at a stirring speed of 1000 rpm respectively.

3.5

LN((XAe-(2*XAe-1))/(XAe-XA)) v/s Time

B(308K) C(318K) D(328K)

3.0

LN((XAe-(2*XAe-1))/(XAe-XA))

2.5

2.0

1.5

1.0

0.5

0.0 0 20 40 60 80 100 120 140 160

Time (min)

Figure 3.8: Typical kinetic plots for the effect of temperature on Un-catalyzed reaction. Speed of agitation = 1000 rpm, mole ratio of acetic acid to methanol = 1:1

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The optimized values of the Un-catalyzed reaction rate constants are presented in Table 3.2 Table 3.2: Reaction rate constants for Un-catalyzed Esterification Temp., K 308 318 328 K3 L.mol-1.min-1 0.015088 0.020076 0.024358 K4 L.mol-1.min-1 2.723251 3.4285 3.707542

The optimized values of the activation energies for Un-catalyzed and Catalyzed reactions are presented in Table 3.3 Table 3.3: Activation Energies for Un-catalyzed and Catalyzed Esterification Reactions Type of Un-Catalyzed Reaction Catalyzed Reaction Reaction Forward Backward Forward Backward E KJ/mol 20.12 12.95 37.626 18.473 IV. Conclusion The esterification reaction of acetic acid with methanol was successfully carried out over Amberlyst-15 as cationic exchange resin as a catalyst and in the absence of catalyst also in stirred batch reactor. The effect of temperature, molar ratios, and catalyst loading on the overall rate of reaction as well as concentration-time profiles were investigated. For catalyzed reaction various experiments were carried out in the temperature range of 308-328K and it has been observed that at 328K conversion was maximum, also catalyst loading varied from 2.5 to 10 wt% and at 10 wt% catalyst loading conversion becomes maximum, similarly if molar ratios varied from 1:1 to 1:3 it has been observed that at molar ratio of 1:3 conversion achieved was maximum. For Uncatalyzed reactions also conversion achieved was maximum at 323K, 1:3 mole ratio. A stirrer speed 800 rpm was found sufficient for eliminating external diffusion. Internal diffusion was negligible under the employed esterification reaction conditions. The conversion of acid increased with increasing temperature and catalyst loading and initial amount of alcohol. The conversion achieved in the non-catalyzed reaction was 14% while in catalyzed reaction it was 54%. To develop the model, reactions are carried out in the temperature ranging between 308 and 328K and molar feed ratio of 1:1. This reaction was intrinsically controlled. A pseudo homogenous kinetic model was employed to fit the experimental data. The activation energies for Un-catalysed forward and backward reactions were evaluated as 20.12 KJ/mol and 12.95 KJ/mol, for the heterogeneous forward and backward reactions were evaluated as 37.626 KJ/mol and 18.473 KJ/mol. V. Nomenclature CA - Concentration of acetic acid mol/lit CB - Concentration of methanol mol/lit CE - Concentration of ester mol/lit CW - Concentration of water mol/lit CAO - Concentration of acetic acid at t=0, mol/lit CBO - Concentration of methanol at t=0, mol/lit E - Activation energy KJ/mol K1 - Rate constant for the heterogeneous forward reaction, lit/mol min K2 - Rate constant for the heterogeneous backward reaction, lit/mol min K3 - Rate constant for the uncatalyzed forward reaction, lit/mol min K4 - Rate constant for the uncatalyzed backward reaction, lit/mol min kc - Equilibrium constant rA - Initial rate mol/lit min R - Real gas constant T - Reaction temperature, K XA - Fractional conversion of acetic acid XB - Fractional conversion of methanol XAe - Fractional conversion of acetic acid at equilibrium VI.
1. 2.

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