caceran0.0in. A sionis cdisy an
unds.tergenroutessive re
tion bylic mehey prtics of
using heterogeneous sulfonic ion exchange resin as the catalyst. Liu et al.
othermal batch reactorrved that the rate con-t and the reaction ratealso observed that the
Chinese Journal of Chemical Engineering 23 (2015) 100105
Contents lists available at ScienceDirect
Chinese Journal of Ch
e lsusing homogeneous sulfuric acid as a catalyst while carrying out the re-action in a reactive distillation unit. The kinetic model shows nonlinear
catalyst activity is slightly inhibited by the formation of water in thereaction mixture. The reaction kinetics and chemical equilibrium ofdependence on the catalyst concentration without the kinetic parame- the reversible catalytic esterication of acetic acid with methanoland Smith [4] found that the kinetics of acid catalyzed esterication ofn-aliphatic acid with methanol is inuenced by the length of carbonchains with different buffer solutions.
Agreda et al. [5] proposed a rate expression for esterication reaction
withmethanol using sulfuric acid catalyst in an iswas investigated by Ganesh et al. [12]. They obsestant is inuenced by the concentration of catalysincreases with the catalyst concentration. Theycatalyst was investigated by Ronnback et al. [3], where the protonationof carboxylic acid was considered as the rate-initiating step in the reac-tion mechanism. They observed that hydrogen iodide was esteriedby methanol and produced methyl iodide as a by-product. Hilton
homogeneous catalysts show similar reaction inhibition by waterformation, and suggested a common reaction mode based on Bronstedacid sites.
The kinetics of reversible liquid-phase esterication of acetic acidters reported. Engell and Fernholz [6] and Krukineticmodel proposed byAgreda et al. [5] for
Corresponding author.E-mail address:[email protected] (M. Mekal
http://dx.doi.org/10.1016/j.cjche.2013.08.0021004-9541/ 2014 The Chemical Industry and Engineerinesterication reaction bynetics of esterication ofneous hydrogen iodide
with methanol were described by Liu et al. [11]. They presented thekinetics using a commercial naon/silica nano composite catalyst(SAC-13) and H2SO4 separately, reported that heterogeneous andusing hydrochloric acid as the catalyst. The kiacetic acid with methanol using a homogeCarboxylic acid esters constitute mnatural products and synthetic composofteners, emulsiers, dispersants, deand biodiesel fuels. Several syntheticcarboxylic acid esters. A comprehenroute is available [1].
The kinetics of esterication reacmethanol in alcoholic and non-hydroxlier by Rolfe and Hinsshelwood [2]. Tbased on the theory of molecular statisThey are widely used asts, surfactants, solventsare available to obtainview of ester synthesis
etween acetic acid anddia was investigated ear-oposed a kinetic model
ing a linear kinetics on catalyst concentration. Elgue et al. [9] alsoproposed a linear kinetics on catalyst concentration and applied it forintensication of methyl acetate production in a continuous reactor.The catalytic esterication reaction between methanol and acetic acidfor the synthesis of methyl acetate with Amberlyst-15 (dry) as hetero-geneous catalyst was studied by Ismail et al. [10] in the temperaturerange of 318338 K. The similarities and differences between heteroge-neous and homogeneous catalyzed esterication reactions of acetic acidajor components of numerous[8] developed a rate expression for the esterication reaction of metha-nol with acetic acid using homogeneous sulfuric acid catalyst, present-1. IntroductionCatalysis, Kinetics and Reaction Engineering
Kinetics of esterication of methanol and ahomogeneous acid catalyst
Mallaiah Mekala , Venkat Reddy GoliDepartment of Chemical Engineering, National Institute of Technology, Warangal 506004, India
a b s t r a c ta r t i c l e i n f o
Article history:Received 17 April 2013Received in revised form 2 July 2013Accepted 5 August 2013Available online 13 November 2014
Keywords:EstericationHomogeneous catalystKinetic rate-equationSimulation
In this work, esterication ofstudied in the temperatureconcentrations ranging fromis varied from 1:1 to 1:4. Thereaction rate are investigatedforward and backward reactThe developed kinetic modelfor the simulation of reactive 2014 The Chemical Industr
j ourna l homepage: www.el et al. [7] modied thethe esterication reaction
a).
g Society of China, and Chemical Indetic acid with mineral
tic acid and methanol to synthesize methyl acetate in a batch stirred reactor isge of 305.15333.15 K. Sulfuric acid is used as the homogeneous catalyst with633molL1 to 0.3268 molL1. The feedmolar ratio of acetic acid to methanoluences of temperature, catalyst concentration and reactant concentration on theecond order kinetic rate equation is used to correlate the experimental data. Therate constants and activation energies are determined from the Arrhenius plot.omparedwith the models in literature. The developed kinetic equation is usefultillation column for the synthesis of methyl acetate.d Engineering Society of China, and Chemical Industry Press. All rights reserved.
emical Engineering
ev ie r .com/ locate /CJCHEwere investigated by Popken et al. [13]. The reaction was catalyzedhomogeneously by acetic acid itself and heterogeneously by an acidicion-exchange resin.
Without catalyst it requires very long time to reach equilibrium [13].Although acetic acid itself may act as a catalyst, its activity for reaction is
ustry Press. All rights reserved.
The experimental results for conversion of acetic acid at differenttemperatures with xed catalyst concentration (0.1288 molL1) areshown in Fig. 1. The rate of conversion of acetic acid increases with tem-perature. At the lowest temperature (305.15 K), the reaction reachesequilibrium after 400 min and at higher temperature, and the time re-quired for the reaction to reach equilibrium reduces drastically. At333.15 K the time needed is only 100min. The higher the reaction tem-perature, the shorter the time required to reach equilibrium. At equilib-rium, the acetic conversion is 0.69 or 69%.
acetic acid at a xed temperature of 323.15 K. As the catalystconcentration increases the reaction reaches equilibrium faster. At0.3268 molL1 catalyst concentration the reaction takes about70 min to reach equilibrium whereas at 0.0633 molL1 it only takesabout 150 min. The effect of catalyst concentration on the acetic acidconversion is similar to that of the effect of temperature.
101M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105very low due to its weak acidic nature. The addition of catalyst improvesthe acidic nature of the reaction mixture by providingmore H+ ions forthe reaction. Homogeneous catalysts such as hydrochloric acid, hydro-gen iodide, hydrogen bromide and sulfuric acid have been used for theesterication reaction between acetic acid and methanol. It is reportedthat sulfuric acid is a better catalyst due to its greater density of acidsites per gram and it can prevent the side reactions [11]. It is more effec-tive than the heterogeneous catalyst for the esterication reaction, so itis selected for the present study.
Although a large number of studies are available in literature, someuncertainties remain in the reported kinetic models. In the presentpaper, the esterication reaction of acetic acid with methanol to pro-ducemethyl acetate using homogeneous sulfuric acid catalyst is studiedat different temperatures, catalyst concentrations and feedmolar ratios.The kinetic models based on concentration as well as activity are devel-oped and the model predictions are compared with experimental data.The model predictions are also compared with the models in literature.
2. Experimental
2.1. Chemicals
Acetic acid (99.95%, bymass), methanol (99%, bymass), and sulfuricacid (98%, by mass) were purchased from SD Fine Chemicals Ltd.(Mumbai, India) and used without any further purication.
2.2. Experimental setup
The esterication reaction was carried out in a 500 ml three neckround-bottom ask placed in a heating rota mantle, which contains aheating knob and a speed control knob. The rota-mantle was main-tained at constant temperature by adjusting the heating knob. Theminimum stirring speedwasmaintained at 240rpm for uniformmixingof catalyst in the reaction mixture using the speed control knob. A glassthermometer inserted into the reactorwasused tomeasure the reactionmixture temperature inside the ask. A spiral condenser was connectedvertically to the reaction ask to reduce the vapor losses from thereactor.
2.3. Experimental procedure
In the experiment, equimolar quantities of methanol (32 g) andacetic acid (60 g) were charged to the reactor. The desired amount orconcentration of sulfuric acid was added to initiate the reaction. Whenthe reaction mixture reached the desired reaction temperature, thetime was noted. The samples were withdrawn at regular intervals oftime and analyzed for the acetic acid concentration. The reactionwas carried out for sufcient time to reach equilibrium conversion orwithout further decrease in acetic acid concentration.
2.4. Analysis
The acetic acid concentration was determined by titration of reac-tion mixture sample with standard solution of NaOH using phenol-phthalein as the indicator. To prepare the standard solution of NaOH,pure water was obtained from an ultra-pure water purier system(Millipore-Synergy UV system) with a resistance of 18.2 M.
3. Results and Discussion
The present esterication reaction with homogeneous catalyst is in-vestigated at 1:1mole ratio of acetic acid tomethanol, with the temper-ature varied from 305.15 to 333.15 K and the catalyst concentration
1 1varied from 0.0633 molL to 0.3268 molL .3.1.3. Effect of initial reactant mole ratioFig. 3 shows the effect of initialmolar ratio of acetic acid tomethanol
on the acetic acid conversion at xed catalyst concentration of 0.12881
Fig. 2. Effect of catalyst concentration on reaction kinetics at 323.15 K. 0.0633 molL1; 0.1288 molL1; 0.1923 molL1; 0.2576 molL1; 0.3268 molL1.3.1.2. Effect of catalyst concentrationFig. 2 shows the effect of catalyst concentration on the conversion of
Fig. 1. Effect of temperature on reaction kinetics at 0.1288molL1 catalyst concentration. 305.15 K; 313.15 K; 323.15 K; 333.15 K.3.1. Effect of different factors on the reaction
3.1.1. Effect of temperaturemolL and reaction temperature of 333.15 K. The equilibrium
terms of acetic acid conversion, XA = 1 CA / CA0. The rate equationis modied as
rA CA0dXAdt
k fC2A0 1XA 2X2AKeq
!: 2
Eq. (2) is integrated and re-arranged to a linear form to nd the for-ward reaction rate constant. The equation is
ln2m22m1XA2m22m1XA
2m22m2
m2k fCA0t 3
where m1 1 1Keq
andm2 21m1
p.
From Eq. (3), the forward reaction rate constants at different tem-peratures and at 0.1288 molL1 catalyst concentration are calculated.The temperature dependency of the reaction rate constants is expressedby the Arrhenius equation.
kb kb0 expEbRT
4b
where kf0 and kb0 are the pre-exponential factors, Ef and Eb are the acti-vation energies for forward and backward reactions, respectively, R isthe gas constant, and T is the temperature.
The inuence of temperature on the reaction rate constant is deter-mined by tting kf and kb to the Arrhenius Eqs. (4a) and (4b). Fig. 4shows the Arrhenius plot of lnkf vs. 1/T and lnkb vs. 1/T. The forward andbackward activation energies are found to be 62,721 and 62,670Jmol1, respectively. Because the two activation energies are nearlyequal, it can be concluded that the equilibrium constant (Keq) for this re-action is nearly independent of temperature [5], and is approximatelyequal to 5.07. The equilibrium constant can be determined experimental-ly from the equilibrium conversion XAe of acetic acid as follows
Keq XAe 2
1XAe 2: 5
Fig. 2 shows the effect of catalyst concentration on the reactionkinetics for ve different catalyst concentrations at xed temperatureof 323.15 K. With similar experiments conducted for various catalystconcentrations at different temperatures to the rate constant kf, andthe pre-exponential factor kf0 are determined. The pre-exponential fac-tor (kf0) is plotted as a function of catalyst concentration as shown inFig. 5. A mathematical expression is proposed from the linear tting ofdata,
kf0 3:0 108 WC 8 107 6
102 M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105k f k f0 expE fRT
4aconversion of acetic acid increaseswithmole ratio due to the availabilityof excess methanol. With an increase in mole ratio of acetic acid tomethanol from 1:1 to 1:4, the equilibrium conversion of acetic acidincreases from 69% to 91.7%.
3.2. The kinetic model
3.2.1. Concentration based modelA second-order elementary kinetic model is assumed since the reac-
tion is carried out with a molar ratio of 1:1 of acetic acid to methanol.The reaction rate expression for the homogeneous reaction [14] is
rA dCAdt
k fCACBkbCCCD k f CACBCCCDKeq
!1
where CA, CB, CC and CD are the acetic acid,methanol,methyl acetate andwater concentrations, respectively, kf and kb are the forward and back-ward reaction rate constants, respectively, and Keq is the equilibriumconstant of the reaction. It is assumed that products water and methylacetate are not present at the beginning of the reaction. The reactionvolume during the reaction remains constant. Eq. (1) is rearranged in
Fig. 3. Effect of reactant initial mole ratio on the acetic acid conversion at 0.1288 molL1
catalyst concentration and reaction temperature 333.15 K. 1:1; 1:2; 1:3; 1:4.Fig. 4. Arrhenius diagram for reaction rate constants.Fig. 5. Relation between pre-exponential factor and catalyst concentration.
usuarioResaltado
usuarioResaltado
usuarioResaltado
usuarioResaltado
usuarioResaltado
usuarioResaltado
usuarioResaltado
usuarioResaltado
3.2.2. Activity modelThe activity model accounts for the non-ideality of the solution. It
can be developed from the concentration-based model by dening theactivity as
ai ixi iCi=Ct : 7
The reaction rate equation in terms of the activities is given by
rA kfact aAaBaCaDKeqact
8
with
Keqact xeqC x
eqD
eqC
eqD
xeqA xeqB
eqA
eqB
: 9
Fig. 7 shows the comparison for the conversion of acetic acid fromexperimental results with that predicted from the activity basedmodel at different catalyst concentrations at 323.15 K. The deviation is
The experimental results and the activity-based model predictedvalues are plotted for acetic acid conversion with constant catalyst con-centration of 0.1288 molL1 and different reaction temperatures asshown Fig. 8. The predicted and experimental values matchwell exceptat lower temperature. As the temperature increases the reaction ratealso increases, which may be due to the increase in the kinetic energiesresulting in more inter-molecular collisions.
Fig. 9 compares the experimental conversion of acetic acid with that
conversion of acetic acid at different catalyst concentrations at 323.15 K. 0.0635molL1; 0. 1288 molL1; 0.3268 molL1; 0.0635 molL1; 0.1288molL1; 0.3268 molL1 (symbols represent experimental data and linesrepresents concentration based model results).
Table 2UNIQUAC interaction parameters
i j aij bij cij
Acetic acid Methanol 390.26 0.97039 3.0613 103Methanol Acetic acid 65.245 2.0346 3.1570 103Acetic acid Methyl acetate 62.186 0.43637 2.7235 104Methyl acetate Acetic acid 81.848 1.1162 1.3309 103Acetic acid Water 422.38 0.051007 2.4019 104Water Acetic acid 98.120 0.29355 7.6741 105Methanol Methyl acetate 62.972 0.71011 1.1670 103Methyl acetate Methanol 326.20 0.72476 2.3547 103Methanol Water 575.68 3.1453 6.0713 103Water Methanol 219.04 2.0585 7.0149 103Methyl acetate Water 593.70 0.010143 2.1609 103Water Methyl acetate 265.83 0.96295 2.0113 104
Fig. 7. Comparison of experimental results with activity-based model results for the con-version of acetic acid at different catalyst concentrations at 323.15 K. 0.0635molL1;0.1288 molL1; 0.3268 molL1; 0.0635 molL1; 0.1288 molL1;
0.3268molL1 (symbols represent experimental data and lines represents activitybased model results).
103M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105Based on the equilibrium conversion, the activities and mole frac-tions are computed and substituted into Eq. (9) to nd the equilibriumconstant based on activity. kfact is related to the temperature through anArrhenius relation
kfact kfact0 exp E fRT
10
with
kfact0 k f0C
2t
eqA eqB
11
where kf0 is calculated from the concentration-based model. The non-where WC is the concentration of catalyst (molL1) in the initialreaction mixture.
Fig. 6 shows the comparison of acetic acid conversion from experi-mental results with that from the concentration basedmodel for differ-ent catalyst concentrations at 323.15 K. As the catalyst concentrationincreases, the conversion of acetic acid increases. At lower catalystconcentrations, the model predictions are in close agreement with ex-perimental results. The predictions are a little lower than experimentalvalues at the early stages but as the time proceeds they are in goodagreement. At higher catalyst concentration the predictions are lowerin magnitude in the initial stage then they tend to approach the exper-imental results closely. One of the reasons for the mismatch is theformation ofwater, whichmay inhibit the rate of reaction until reachingthe equilibrium.
Fig. 6. Comparison of experimental results with concentration basedmodel results for theideality of the reaction mixture is calculated by the UNIQUAC equation.predicted by the concentration basedmodel and activity basedmodel ata xed catalyst concentration of 0.1288 molL1 and different temper-little between the experimental and predicted results, except at lowercatalyst concentrations.The UNIQUAC ri and qi values and the interaction parameters are givenin Tables 1 and 2, respectively [12].
Table 1UNIQUAC ri and qi values
Component ri qi
Acetic acid 2.2024 2.0720Methanol 1.4311 1.4320Methyl acetate 2.8042 2.5760Water 0.9200 1.4000atures. Both models are in good agreement with the experimental data.
usuarioResaltado
usuarioResaltado
usuarioResaltado
The experimental results are quite accurately predicted by our modelsas well as Agreda et al.'s model [5]. The accuracy of the predictions de-creases in the following order: activity-based model, concentrationbased model, Agreda et al.'s model [5], Bonnaillie et al.'s model [15],Elgue et al.'s model [9], and Liu et al.'s model [8].
Fig. 8. Comparison of experimental results with activity- based model results for theconversion of acetic acid at different reaction temperatures at 0.1288 molL1
Fig. 10. Comparison of different kinetic models at 313.15 K and 0.3268 molL1 catalystconcentration. experimental; concentration based; activity based; Liuet al. [8]; Elugu et al. [9]; Bonnaillie et al. [15]; Agreda et al. [5].
104 M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105catalyst concentration. 305.15 K; 313.15 K; 323.15 K; 333.15 K;305.15 K; 313.15 K; 323.15 K; 333.15 K (symbols represent exper-imental data lines represents activity based model results).3.2.3. Comparison with models in literatureThe kinetic models proposed for the esterication of acetic acid
with methanol are given in Table 3. Our experimental data and modelpredictions are compared with these literature models as shown inFigs. 1012.
Fig. 10 shows the conversions of acetic acid from the concentrationand activity based models and the existing kinetic models in literatureat temperature 313.15 K and catalyst concentration of 0.3268 molL1.
Fig. 11 shows the comparison of the experimental results againstkinetic models at temperature of 323.15 K and catalyst concentrationof 0.3268 molL1. The experimental results are predicted fairly accu-rately by the activity-based, concentration-based and Agreda et al.'smodels. The activity-based model provides a slightly better t than
Fig. 9. Comparison of experimental results with respect to concentration and activity-based model results for the conversion of acetic acid at different reaction temperaturesat 0.1288 molL1 catalyst concentration. 305.15 K; 313.15 K; 323.15 K; 333.15 K (symbols represent experimental data); 305.15 K; 313.15 K;323.15 K; 333.15 K (activity based model); 305.15 K; 313.15 K; 323.15 K; 333.15 K (concentration based model).
Table 3Kinetic models and parameters in literature
No Kinetic model
1 rA kf exp EfRT
CACB CCCDKeq
kf k1 WC 2 k2WC forWC0:004kf k3k4 exp k5WC0:004
forWCN0:004
2 rA WC 0:38CD
CACB CCCDKeq
3 rA WC kf exp E fRT
CACBkb expEbRT
CCCD
h i
4 rA WC kf exp EfRT
CACBkb expEbRT
CCCD
h i
Note: the units of kf and kb are Lmol1min1; E1 and E2 are Jmol1.Parameters Reference
Keq = 5.2 [5]
Keq = 6.22 at 333.15 K [8]
kf = 4.21kb = 0.322Ef = 53,800Eb = 52,580
[9]
kf = 0.0055kb = 0.011Ef = 41,800Eb = 41,800
[15]
Fig. 11. Comparison of different kinetic models at 323.15 K and 0.3268 molL1 catalystconcentration. experimental; concentration based; activity based; Liuet al. [8]; Elugu et al. [9]; Bonnaillie et al. [15]; Agreda et al. [5].
the concentration-based model. Comparing Fig. 11 with Fig. 10, we canconclude that even at higher temperatures, while maintaining the cata-lyst concentration constant, activity-based and concentration-basedmodels predict the results with reasonable accuracy.
Fig. 12 compares the available kinetic models [5,8,9,15], our modelsand the experimental data at temperature of 323.15 K and catalyst con-centration of 0.1288 molL1. The models proposed in the presentstudy, concentration-based and activity-based models, are better thanthe models available in the literature. Our models provide better t tothe experimental data.
4. Conclusions
The esterication reaction between methanol and acetic is conduct-ed in a batch stirred reactor with sulfuric acid as a catalyst. The experi-mental results show that as the temperature and catalyst concentrationincrease the reaction rate increases. The experimental data is expressedwith a reversible second order reaction rate equation. The activationenergies for forward and backward reactions are obtained using theArrhenius equation. A mathematical equation is developed to describethe relation between the catalyst concentration and the frequencyfactor. The kinetic models are developed for the concentration-basedand activity-based and comparedwith literaturemodels. The developedkinetic equation predicts the results accurately.
Nomenclatureai activity of component iCA acetic acid concentration, molL1
CA0 initial acetic acid concentration, molL1
CB methanol concentration, molL1
CC methyl acetate concentration, molL1
CD water concentration, molL1
CAe, CBe,CCe and CDe equilibrium concentration of acetic acid,methanol,
methyl acetate and water, molL1
Eb backward activation energy, Jmol1
Ef forward activation energy, Jmol1
Keq equilibrium constantkb backward reaction rate constant, Lmol1min1
kb0 backward frequency factor, L mol1 min1
kf forward reaction rate constant, Lmol1min1
kf0 forward frequency factor, Lmol1min1
rA reaction rate of acetic acid, molL1min11 1
242 (2006) 278286.[12] B. Ganesh, K. Yamuna Rani, B. Styavthi, Ch. Venkateswrlu, Development of kinetic
105M. Mekala, V.R. Goli / Chinese Journal of Chemical Engineering 23 (2015) 100105Fig. 12. Comparison of different kinetic models at 323.15 K and 0.1288 molL1 catalystconcentration. experimental; concentration based; activity based; Liuet al. [8]; Elugu et al. [9]; Bonnaillie et al. [15]; Agreda et al. [5].models for acid-catalyzed methyl acetate formation reaction: Effect of catalystconcentration and water inhibition, In. J. Chem. Kinet. 43 (5) (2011) 263277.
[13] T. Popken, L. Gotze, J. Gmehling, Reaction kinetics and chemical equilibrium ofhomogeneously and heterogeneously catalyzed acetic acid esterication withmethanol and methyl acetate hydrolysis, Ind. Eng. Chem. Res. 39 (2000) 26012611.
[14] O. Levenspiel, Chemical Reaction Engineering, 3rd edition John Wiley &Sons, 1999.[15] L. Bonnaillie, X.M.Meyer, A.M.Wilhelm, Teaching reactive distillation: Experimental
results and dynamic simulation of a pedagogical batch pilot-plant, Proceedings ofIMSR2, Nuremberg: Germany, 2001.R gas constant, Jmol KT absolute temperature, Kt time, minWC catalyst concentration, molL1
XA acetic acid conversionXAe acetic acid equilibrium conversioni activity coefcient of component i
References
[1] G.D. Yadav, P.H. Mehta, Heterogeneous catalysis in esterication reactions: Prepara-tion of phenethyl acetate and cyclo-hexyl acetate by using a variety of solid acidiccatalysts, Ind. Eng. Chem. Res. 33 (1994) 21982208.
[2] C. Rolfe, C.N. Hinsshelwood, The kinetics of the esterication reaction betweenacetic acid and methanol, Trans. Faraday Soc. 30 (1934) 935944.
[3] R. Ronnback, T. Sami, A. Vuori, H. Haario, J. Lehtonen, A. Sundqvist, E. Tirronen,Development of a kinetic model for the esterication of acetic acid with methanolin presence of homogenous catalyst, Chem. Eng. Sci. 52 (1997) 33693381.
[4] S. Hilton, H.A. Smith, Kinetics of the catalyzed esterication of normal aliphatic acidsin methyl alcohol, J. Am. Chem. Soc. 61 (1939) 254.
[5] V.H. Agreda, L.R. Partin, W.H. Heiss, High puritymethyl acetate via reactive distillation,Chem. Eng. Process. 86 (2) (1990) 4046.
[6] S. Engell, G. Fernholz, Control of a reactive separation processes, J. Mol. Catal. A Chem.245 (2006) 132140;Chem. Eng. Process. 42 (2003) 201210.
[7] L.U. Kreul, A. Gorak, C. Dittrich, P.I. Barton, Dynamic catalytic distillation: Advancedsimulation and experimental validation, Comput. Chem. Eng. 22 (1998) S371S378.
[8] Y. Liu, E. Lotero, J.G. Goodwin Jr., Effect of water on sulfuric acid catalyzed esterica-tion, J. Mol. Catal. A Chem. 245 (2006) 132140.
[9] S. Elgue, A. Devatine, L.E. Prat, P. Cognet, M. Cabassud, C. Gourdon, F. Chopard, Inten-sication of ester production in a continuous reactor, Int. J. Chem. React. 7 (A24)(2009) 116.
[10] S.K. Ismail, H.Z. Tergioglu, U. Dramur, Catalytic esterication methyl alcohol withacetic acid, Chin. J. Chem. Eng. 9 (1) (2001) 9096.
[11] Y. Liu, E. Lotero, G.J. Goodwin Jr., A comparison of the esterication of acetic acidwith methanol using heterogeneous versus homogeneous acid catalysis, J. Catal.
Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst1. Introduction2. Experimental2.1. Chemicals2.2. Experimental setup2.3. Experimental procedure2.4. Analysis
3. Results and Discussion3.1. Effect of different factors on the reaction3.1.1. Effect of temperature3.1.2. Effect of catalyst concentration3.1.3. Effect of initial reactant mole ratio
3.2. The kinetic model3.2.1. Concentration based model3.2.2. Activity model3.2.3. Comparison with models in literature
4. ConclusionsNomenclatureReferences