The kinetics of the esterification of n-butanol with acetic acid
have been studied in a batch and in a tubular reactor. The best
model for obtaining the esterification rate with a partially wet ion
exchanger (270/o water contents) is obtained by assuming a pseudohomogeneous
system, while the kinetics of dry ion exchangers is
best represented by a model derived from assumptions based on a
heterogeneous system.
A separate study of the induction period in a tubular reactor
shows the considerable influence of the water content on reaction
kinetics. This is manifested by a change of the catalytic activity
during the reaction. Change of the catalytic activity can lead to
erroneous interpretation of experimental results and to derivations
of inadequate kinetic expression. It is shown that change of
ion exchanger activity in the induction period is caused by diffusion
of reactants into resin particle

S . Zrnčević

Z. Gomzi

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C'.ROATICA CHEMICA ACTA CCACAA 53 (1) 25-32 (1980) CCA-1185 YU ISSN 0011-1643 UDC 541.128 Qriginal Scientific Paper Esterificatfon of n-Butanol with Acetic Acid Catalyzed by a Cation Exchange Resin Effect of the Catalytic Activity on Reaction Kinetics Z. Gomzi and S . Zrncevic Faculty of Technology, University of Zagreb, Zagreb, Croatia, Yugoslavia Received May 25, 1979 The kinetics of the esterification of n-butanol with acetic acid have been studied in a batch and in a tubular reactor. The best model for obtaining the esterification rate with a partially wet ion exchanger (270/o water contents) is obtained by assuming a pseudo-homogeneous system, while the kinetics of dry ion exchangers is best represented by a model derived from assumptions based on a heterogeneous system. A separate study of the induction period in a tubular reactor shows the considerable influence of the water content on reaction kinetics. This is manifested by a change of the catalytic activity during the reaction. Change of the catalytic activity can lead to erroneous interpretation of experimental results and to derivat-ions of inadequate kinetic expression. It is shown that change of ion exchanger activity in the induction period is caused by dif-fusion of reactants into resin particle. INTRODUCTION The kinetics of esterification with ion exchangers in a liquid phase have been investigated for numerous reactions. There is, at present, no unified opinion about the kinetics of these reactions. The majority of the authors prefers Helfferich's classical explanation which states that the liquid phase catalysis with ion exchangers is pseudohomogeneous1- 3. Kinetic expressions derived from this assumption correspond to formulas used for homogeneous catalytic systems. Only several authors have tried to explain the kinetics as heterogeneous catalytic reactions4•5• Experimental results obtained by a number of investigators show that the initial reaction time in batch reactors can be explained by the pseudo-homogeneous model6•7 • Dissagreement between the pseudohomogeneous model and the data has been explained in several ways. The reaction kinetics in the induction period is explained by introducing the assumpUon that the ion exchangers have a special structure and by the transport phenomena which accompanies sorption of the reactants8•9• It should be noted that liquid phas12 dehydrations with ion exchangers are usually considered as heterogeneom catalytic reactions9•10• Gates at al.8 assumed a shrinking core model for the induction period of dehydration of the t-butyl alcohol. According to their assumptions, the reaction 26 Z. GOMZI AND S. ZRNCEVIC rate is essentially determined by the water content in the resin and the reacting mixture. They used macroreticular and standard ion exchangers. The induction period was determined only with the standard resin. Absence of the induction period in experiments with a macroreticular ion exchanger were ascribed to a large internal surface and to the absence of diffusion effects within the resin particle. In a subsequent work7 the authors state that reaction in the absence of water was catalyzed by fixed -S03H groups in a macroreticular ion exchanger. Water added to the reactant (t-butyl alcohol) competed for -S03H groups inhibiting the reaction. After more water was added the reaction was cata-lyzed by hydrated protons in a resin matrix. The global rate is represented by an equation assuming rates at high and low water content. This work deals with the adequacy of the heterogeneous and pseudo homogeneous model for the esterification of n-butanol with acetic acid by means of a standard ion exchanger. Experiments were carried out in a batch reactor with both dry and wet resin. The induction period was investigated separately in a tubular reactor. EXPERIMENTAL METHODS Experiments were carried out with a commercial ion exchanger Ionenaustauscher I (cation microporous resin on the base of polystyrene with 80/o DVB as crosslinking agent). Prior to an experiment, the ion exchanger was converted in H+ form 12 and a part of it was dried for 24 hours at 115 °c, the rest was dried in air to 270/o water. A three necked flask was used as a batch reactor. It was equiped with a mechanical stirrer and a thermometer. A constant temperature of 55 °c was maintained by an ultrathermostat. A tubular reactor assembly shown in Figure 1. was used to study the induction period at 55 °c. Apart from measuring the acid concentration, the level of the resin bed in the reactor was measured. Reaction mixtures in both cases were analyzed by titrating acetic acid with NaOH in the samples. RESULTS AND DISCUSSION Two sequences of experiments were carried out in the batch reactor, one with the partially dry resin (270/o water} and the other with the com-pletely dry ion exchanger. In both cases the amount ·of resin and the initial reactant ratios were varied from 2 to 8 g and 0.1 to 10, respectively. Study of the induction period in the tubular reactor was carried out with the initially dry ion exchanger, quantities varied between 2 to 8 g and flow rates between 1 to 3 ml/min. Kinetic analysis Pseudohomogeneous system assumption. Kinetic expressions of irrever-sible first and second order reaction, as well as second order reversible reaction have been tested. Such models are used for the ki:netics of esterificahon in homogeneous systems. Heterogeneous system assumption. Models based on Hougen- Watson-kinetics have been selected. Active siites in the ion exchangers are H• ions in -S03H groups. Reaction occurs in the adsorbet layer between H+ ions and reactants. Ester is produced through several intermediate steps. It was assumed that the basic reaction mechanism is identical to the one in the homogeneous systems11 . Hence, the following monomolecular mechanism (AA C1) is proposed: ESTERIFICATION WITH ION EXCHANGER 27 <f) lo CF-7 11 ..!.. 4 Figure 1. Tubular reactor assembly. 1 - tubular reactor, 2 - thermostated chamber, 3 -preheater section, 4 - ultrathermostat, 5 - water cooled condenser, 6 - capillary, 7 - reactan1 storage, 8 - contact manometer, 9 - electromagnetic valve, 10 - relais, 11 -pressured air. RCOOH + H + ~ RCoo+H~ RCoo+H2 ~ Rco+ + H20 Rco+ + RiOH :;:::O: RCoo+HR1 RCoo+HR1 :;:::O: RCOOR1 + H + (1) (2) (3) (4) In a bimolecular mechanism (AA C2) which is more probable, reactions (2) and (3) occur simultaneously, i.e. (5) From the point of view of the heterogeneous catalysis, the reactions (1) and (4) correspond to chemisorption of the acetic acid and desorption of pro-28 Z. GOMZI AND S. ZRNCEVIC duced ester, while reactions (2), (3) and (5) correspond to the surface reactions (in , the adsorbed layer) between chemisorbed acid and alcohol. Alcohol can either be adsorbed or is present in the liquid phase. Based on these assumptions, a number of mechanisms can be assumed, depending on which of the reactions in the proposed reaction scheme are considered to be much slower than the others. The simplest plausible models that have been selected are given in Table I. TABLE I Heterogeneous System Assumption. Models Based on Hougen - Watson kineti~s. CA; CB, Cc - Concentration of Acid, Alcohol and Water Respectively, k - Rate Constant, Ki, K 2, K 3 - Adsorption Equilibrium Constants of Acid, Alcohol and Water i Eq. no. 1 2 3 4 5 Model Corresponds to Monomolecular surface reaction. Strong adsorption of acid. Bimolecular reaction between adsorbed acid and alcohol from fluid phase. Strong adsorption of water. Bimolecular reaction between adsorbed acid and alcohol from fluid phase. Strong adsorption of acid. Bimolecular surface reaction between acid and alcohol. Strong adsorption of acid. Bimolecular surface reaction between acid and alcohol. Strong adsorption of acid and alcohol. Only models with three parameters at the most have been chosen (k 1 - k8 ) , even though a number of more complicated models could have been employed. However, the true values of the constants in the multiparameter models are difficult to determine if there is only one variable (in this case concentration). Calculations were made on a UNIVAC 1110 computer at the Computer Centre of the University of Zagreb. The computer program contained: a) fitting of experimental data XA-time to a sixth order polynomial, b) reaction rate calculation from the polynomial for given conversion and time, c) parameter estimation algorithm. Objective functions were defined as a sum of squares of differences between calculated reaction rates from the experimental data and the predicted rates from the mathematical models. Marquardf s algorithm was used as the optimization routine. It is applicable for nonlinear estimation problems and is known to have excellent convergence properties in a broad parameter range. The selection of the best model was based on the comparison of standard deviations of reaction rates for different models. Altogether we performed 30 ESTERIFICATION WITH ION EXCHANGER 29 experiments, 16 with the dry and 14 with the wet ion exchanger. ·, Table II shows the calculated average standard deviation from all exp~riments for eight chosen mathematical models (three for the homogeneotis and five for the heterogeneous system). TABLE II Calculated Standard Average Deviations of Selected Models for Experiments with Wet and Dry Ion Exchangers Model (Javf aav' min dry wet irreversible reaction first order 2.69 3.53 irreversible reaction second order 2.67 3.41 reversible reaction second order 2.88 1.00 heterogeneous model No. 1 4.50 3.90 No. 2 2.01 3.76 No. 3 1.89 3.38 No. 4 1.00 3.42 No. 5 1.92 3.44 The table shows that the model no. 4 has the minimum average standard deviation for expel'iments with the dry ion exchanger, while the model based on second order reversible reaction is the best approximation of the data obtained with the wet ion exchanger. Model 4 describes a heterogeneous reaction with the slowest step being the surface reaction between chemisorbed acid and adsorbed alcohoL The above results demonstrate the significance of water content in the resin prior to an experiment. Different kinetic interpretations of the esteri-fication reactions given by the previous authors can pe probably attributed to this fact. Tartarelli at al.1 used a simple second order irreversible reaction to describe esterification of n-butanol with olernic acid with the air dry ion exchanger. On the other hand, Rodriguez and Setinek5 describe reesterifi-cation of n-propanol with ion exchanger dried in vacuum at 100-120 °C as heterogeneous, assuming that the slowest step is a surface reaction between adsorbed alcohol and ester. In this work, we used the ion exchanger with different initial water content. It can be assumed that different initial water concentration cause different kinetic behaviour. In Figure 2. experimental data are shown, conversion versus 'time (XA - t) , measured in the batch reactor obtained with dry ion exchanger. It is well known that the ion exchanger significantly solvates polar orga-nic and inorganic solvents like alcohols and water. There is also sorption of organic acids. Since the catalytic reaction with dry resin occurs simultaneously with the solvation and sorption, it follows that there is a period of resin 30 30 2.0 10 20 Z . GOMZI AND S . ZRNCEVIC 40 60 80 100 t/min 120 Figure 2. Conversion versus time in batch reactor, equimolar ratio butanol-acetic acid, 55 •c <• - dry resin, 0 - wet resin) . swelling in the reaction mixture. These processes change the initial catalytic activity of resin until some sorption equilibrium steady state is reached. This initial period of salvation of the ion exchanger in a reaction mixture we studied in a tubular reactor. Kinetic analysis of the induction period. Steady state reached in a tubular reactor depends on residence time of the reactants, if all other parameters are constant. The flow rate in experiments was between 1 to 3 ml/min so that the maximal residence time was 10 min. Conversion was measured from the moment of charging the reactor with the catalyst. Also, the time depen-dence of the catalyst bed height was measured. At typical result of an expe-riment is shown in Figure 3. Figure 3. shows that the reactor reaches a steady state in not more than 10 min if the wet ion exchanger already has been used (curve 2), while with dry resin the steady state is reached after 90 min. (curve 1). Steady state conversion is the same, regardless of the initial catalyst state (wet or dry). Hence, the dry catalyst changes its activity during the induction period until an equilibrium state is reached. The shape of curve 1 and 2 shows that the stationary conversion is obtained when the resin hight becomes constant, i. e. ESTERIFICATION WITH ION EXCHANGER .R. 1o 0 <-x 3o 2o lo lo 0 "----t!S'-- -'--------'----- -'-------'------'--- --' 0 0 20 40 60 80 loo ymin 120 Figure 3. Time dependence of the catalyst height and conversion in tubular reactor. 3., ; . when swelling stops. F urthermore, the shapes of the curve are identical and therefore the rate of the activation and the rate of sorption are proportional. The experimental results show the induction period of 90 min. The same period also exists in the batch reactor (Figure 2.) , where simultaneous reaction with activation occurs. However, a kinetic analysis of the batch reactor data has been carried out with the assumption that catalyst activity was constant. Since this assumption is not correct, a good agreement between data approxi-mation, based on such a model and experimental data, does not justify the acceptance of such a model. On the contrary, the experiments with the wet ion exchangers show that the physically most justified model also fitts the data very well. The best agreement of the heterogeneous model for the case with the dry ion exchanger is probably to simultaneous occurence of the chemical reaction and the catalyst activation. Kinetic analysis with the wet and the dry ion exchanger in the batch reactor, and the kinetic analysis of the induction period show that the model based on the pseudohomogeneous system assumption is the most acceptable. Also, the induction period of this reaction depends on the sorption equilibrium between reactants within a resin bed. Acknowledgement. - The authors are greatfull to dr Z. Kurtanjek for developing the computer program. 32 Z. GOMZI AND S. ZRNCEVIC REFERENCES 1. G. Tartar e 11 i, G. Stopp at o, F. More 11 i, A. Lucchesi, and M. G i or-g in i, J. Cata!. 18 (1970) 21!J. 2. N. G. Po 1 ans k ii, and G. V. Go r bun o v, Zh. Prikl. Khim. 45 (1972) 2282. 3. I. C. Y. Ts a o, T. C. Hu a n g, and H. S. Wen g, Ind. Eng. Chem. Process Des. Develop. 7 (1968) 401. 4. M. B. B o ch n er, S. M. Ger b er, V. R. . Vi et h, and A. I. R o d g er, Ind. Eng. Chem. Fundam. 4 (1965) 314. 5. 0. R o d r i g u e z, and K. S et in e k, J. Cata!. 39 (1975) 449. 6. C. L. Levesque, and A. M. Craig, Ind. Eng. Chem. 40 (1968) 96. 7. B. C. Gates and W. Rodriguez, J. Cata!. 31 (1973) 27. 8. H. W. H e at h and B. C. Ga t e s, AIChE J. 18 (1972) 321. 9. B. C. G a t es, J. S. Wis no us k a s, and H. W. H e a th, J. Cata!. 24 (1972) 320. 10. V. J. Fri 1 et t e, E. B. Mower, and M. E. Rubin, J. Cata!. 3 (1964) 25. 11. C. K. Ing o 1 d, Structure and Mechanism in Organic Chemistry, Cornell Univ. Press, Ithaca, New York 1968. 12. I. E. Sa 1 mo n and D. V. Ha 1 e, Ion Exchange a Laboratory Manuel, London 1959. SAZETAK Esterifikacija n-butanola s octenom kiselinom uz kationski izmjenjivac kao katali-zator. Utjecaj aktivnosti katalizatora na kinetiku reakcije z. Gomzi i s. Zrncevic Kinetika esterifikacije n-butanola s octenom kiselinom u tekucoj fazi ispitana je u cijevnom i kotlastom reaktoru. Uz djelomicno mokri (27°/o vode) ionski izmjenji-vac najbolje slaganje daje model izveden iz pretpostavke pseudohomogenosti sistema, dok uz suhi ionski izmjenjivac najbolje slaganje pokazuje kineticki model izveden iz pretpostavke heterogenosti sistema. Posebnim ispitivanjem indukcijskog perioda u cijevnom reaktoru ustanovljen je znaeajan utjecaj vode na kinetiku reakcije. Taj utjecaj oCituje se u promjeni kataliticke aktivnosti katalizatora za vrijeme reakcije sto dovodi do pogresnog koriStenja eksperimentalnih podataka dobivenih u kotla-stom reaktoru u svrhu izvodenja kinetickog izraza. Promjena aktivnosti ionskog izmjenjivaca u indukcijskom periodu uzrokovana je difuzijom reaktanata u zrno ionskog izmjenjivaea. TEHNOLOSKI FAKULTET SVEUCILISTA U ZAGREBU, ZAGREB Prispjelo 25 . svibnja 1979. 

Esterificatfon of n-Butanol with Acetic Acid Catalyzed by a Cation Exchange Resin

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