Ind. Eng. Chem. Res.

2006, 45, 5251-5257

5251

A Kinetic Model for the Esterification of Lactic Acid and Its Oligomers
Navinchandra S. Asthana, Aspi K. Kolah, Dung T. Vu, Carl T. Lira, and Dennis J. Miller*
Department of Chemical Engineering and Material Science, Michigan State UniVersity, East Lansing, Michigan 48824

The kinetics of esterifying lactic acid and its oligomers with ethanol over Amberlyst 15 cation-exchange resin have been determined via batch reaction studies. The kinetic model for esterification of lactic acid and its oligomers uses nth-order, reversible rate expressions for esterification and oligomerization reactions. Rate constants, activation energies, and equilibrium constants were generated via regression of experimental results. Model predictions for esterification of 20%, 50%, and 88% lactic acid solutions in water are in good agreement with experimental results over a wide range of experimental conditions.
1. Introduction We recently reported on the esterification of lactic acid with ethanol to form ethyl lactate in a reactive distillation column.1,2 Reactions were performed using different aqueous solutions of lactic acid as reactants in the presence of Amberlyst 15 cationexchange resin as a catalyst. Water as a reaction product was continuously removed from the column in the column distillate stream, thus driving the reaction toward higher acid conversion and ester yields. Under optimum reaction conditions, >95% acid conversion with 65% yield of ethyl lactate was achieved. At concentrations of >20 wt % in water, lactic acid undergoes oligomerization reactions to form linear oligomer acids. The extent of oligomerization is inversely related to the water content of the solution.3,4 These oligomer acids react with ethanol to yield oligomer esters. In reactive distillation or any other lactic acid esterification scheme, oligomer formation and esterification adversely affect ethyl lactate yield and pose a considerable challenge in predicting process behavior. For accurate design, therefore, it is critical to include and characterize oligomer reactions in the process model. Many reactive distillation models only consider reaction equilibrium.5,6 These reaction equilibrium models are useful in cases where the reaction kinetics are very fast (e.g., where equilibrium is achieved in a short reaction time) but systematically predict higher conversions than those that are obtained experimentally in cases where the reaction kinetics are slow. In those cases, it has been shown that kinetics-based simulations give more accurate and more reliable predictions.7,8 In lactic acid esterification, where a series of relatively slow reactions occurs, a reliable knowledge of the kinetics is, thus, essential to simulate the process effectively. There have been several reports describing the kinetics of lactic acid esterification with different alcohols.9-17 Most of them involve dilute aqueous solutions of lactic acid (e20 wt %),8-11 thus obviating the need to account for oligomers in solution. Others have examined esterification kinetics at high lactic acid concentrations but have not explicitly included the role of oligomers. Engin et al.16 studied the esterification of 92 wt % lactic acid solutions with ethanol, accounting for hydrolysis of oligomer acids but ignoring esterification reactions. Zhang et al.17 made no mention of oligomers in their study of esterification kinetics of 80 wt % lactic acid. The esterification kinetics developed by Tanaka et al.14 represent the only prior
* To whom correspondence should be addressed. Tel.: 1-517-3533928. Fax: 1-517-432-1105. E-mail address: millerd@egr.msu.edu.

work that considers higher oligomer acids and their esters. Although they modeled reaction kinetics and generated rate constants, they did not clearly describe the catalyst quantity used in the reaction, and, thus, their results have limited utility. Furthermore, the limited parametric studies they conducted hinder the applicability of their rate constants to predict composition profiles over a wide range of reaction conditions. Because prior kinetic models do not reliably or completely predict the behavior of lactic acid oligomers and their esters, we have conducted and report here a kinetic study describing rate expressions and rate constants for formation, esterification, and hydrolysis of oligomer acids and esters over a wide range of lactic acid concentrations, alcohol contents, temperatures, and catalyst loadings. The kinetic model presented is useful in both batch and continuous process designs for lactic acid esterification. 2. Experimental Section 2.1. Chemicals and Catalysts. Lactic acid (20 wt % in water), ethyl lactate (97%), high-performance liquid chromatography (HPLC)-grade acetonitrile, 0.1 N NaOH solution, 0.1 N KOH solution, and Amberlyst-15 cationic exchange resin were obtained from Aldrich. A 50 wt % aqueous solution of lactic acid was procured from Purac. Concentrated lactic acid (88 wt % in water), HPLC-grade water, and absolute ethanol were purchased from J.T. Baker. Ethyl lactate was purified to eliminate water prior to use by treating it with 3 molecular sieves (dried at 550 C) and then distilling it under vacuum to obtain 100% purity. The purities of all chemicals were confirmed via gas chromatography (GC). Amberlyst 15 cation-exchange resin, which is a copolymer of divinylbenzene and styrene with 15%-18% cross-linking, is used as the heterogeneous catalyst in this work. The physical and chemical properties of the resin have been well-documented.18 The nitrogen Brunauer-Emmett-Teller (BET) surface area, pore volume (<120 nm pore diameters) and average pore size measurements, as determined in a Micromeritics ASAP 2010 instrument, are 53 m2/g, 0.40 cm3/g, and 30 nm, respectively. The total cation exchange capacity (CEC) of Amberlyst 15 is 4.6 mequiv H+ per g dry resin. The resin was washed and dried at 95 C before its use in reaction. 2.2. Reaction Procedure. The kinetics of esterification involving 88 and 50 wt % lactic acid solutions with ethanol were measured in a stirred glass batch reactor (85 cm3). This reactor was equipped with an outer circulating heating jacket (to maintain constant temperature inside the reactor) that had

10.1021/ie0513604 CCC: $33.50 2006 American Chemical Society Published on Web 06/23/2006

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silicon oil as the circulating fluid. The reactor was also equipped with a condenser, thermocouple, and sampling port. At the start of reaction, the reactor was filled with the desired amount of lactic acid and ethanol and heated to reaction temperature. A catalyst was added to the reactor through one of the reactor ports. The point of catalyst addition was considered as time zero for the reaction. The extent of reaction was followed by sample withdrawal and analysis at regular intervals. All reactions that involved 20 wt % lactic acid, as well as reactions conducted at temperatures of >80 C for 88 and 50 wt % lactic acid, were conducted in a stirred 300-mL Parr batch reactor (Model 4561, Parr Instrument Co.). For each experiment, the reagents and catalyst were charged into the reactor and heated to the reaction temperature. Stirring commenced after the temperature was attained; this was noted as zero reaction time. Samples were withdrawn periodically over the course of the reaction and analyzed. For all reactions, total concentration and conversion of lactic acid is reported on a monomer equivalent basis. The 88 wt % lactic acid solution consists of monomer acid (L1) and linear oligomer dimer acid (L2), trimer acid (L3), and tetramer acid (L4); therefore, the concentrations of L2, L3, and L4 were multiplied by 2, 3, and 4, respectively, and added to the L1 concentration to give the monomer equivalent concentration. 2.3. Analysis. All samples were analyzed for water (W) and ethanol (EtOH) using a Varian model 3700 gas chromatograph that was equipped with a thermal conductivity detector (TCD) and a stainless steel column (4 m 3.25 mm) packed with a liquid stationary phase of Porapak Q. The column oven was subjected to a temperature program that involved heating from 413 K (after a 2-min hold) to 493 K (and held for 6 min) at a rate of 20 K/min. High-purity helium (99.999% pure) was used as the carrier gas at a flow rate of 20 mL/min. The injector and detectors were maintained at 493 K. Lactic acid monomer (L1) and its linear oligomer acids (L2, L3, and L4), ethyl lactate (L1E), and ethyl esters of oligomer acids (L2E, L3E, and L4E) were analyzed using HPLC. A complete description of the analysis methodology is presented in detail elsewhere.1-3 The total acid content was determined by titration with a standard 0.1 N NaOH solution, using phenolphthalein as an indicator, as a check of HPLC results. The results obtained for the acid content from HPLC were comparable to those from titration. 3. Results The base case conditions for reaction included 88 wt % lactic acid feed and ethanol with feed quantities of 0.30 mol of lactic acid (L1 equivalent), 0.2 mol of water (present in 88 wt % lactic acid solution), and 0.97 mol of ethanol, a catalyst loading of 3 wt % of total reactant weight, a temperature of 80 C, and an agitation speed of 740 rpm. To cover a broad range of conditions, esterification reactions were also performed on solutions containing 20, 50, or 88 wt % lactic acid (compositions provided in Table 1) using ethanol:lactic acid molar feed ratios from 1:1 to 4:1, catalyst loadings from 0 wt % to 5 wt %, and reaction temperatures from 335 K to 363 K. The results of these experiments were used in the regression analysis of the kinetic model (described below) to determine an optimum set of rate constants that describe esterification. Representative results from experiments and from the kinetic model are represented in Figures 1-6 by data points and dotted lines, respectively. Because the 88 wt % lactic acid solution contains the highest concentrations of oligomers (Table 1) and, thus, represents the

Figure 1. Effect of the ethanol:lactic acid initial molar ratio (MR) on conversion. Reaction conditions: 88 wt % lactic acid solution, catalyst loading ) 3 wt %, agitation rate ) 740 rpm, and reaction temperature ) 80 C. Dotted lines are model fit; symbols represent experimental data (([) MR ) 1, (2) MR ) 2, (9) MR ) 3, and (b) MR ) 4). Table 1. Composition of Lactic Acid Feedstocks
Feed Designation (Nominal) parameter feed component L1 L2 L3 L4 H2O monomer equivalent concentration 20 wt % lactic acid 23 wt % (5.6 mol %) 50 wt % lactic acid 46 wt % (15.2 mol %) 3 wt % (0.5 mol %) 88 wt % lactic acid 58 wt % (43.5 mol %) 22 wt % (9.2 mol %) 6 wt % (1.8) 2 wt % (0.4) 12 wt % (45.1 mol %) 10.8 M

77 wt % (94.4 mol %) 2.6 M

51 wt % (84.3 mol %) 5.9 M

most-complex reaction mixture, the results from its esterification are presented in detail here. 3.1. Effect of Reactant Molar Ratio. The effect of the ethanol:lactic molar feed ratio was studied over the range of 1:1 to 4:1. An increase in lactic acid conversion was observed with increasing molar ratios (Figure 1) up to 3:1. Little enhancement in acid conversion was observed when the feed molar ratio was increased from 3:1 to 4:1; therefore, most reactions were conducted at a feed molar ratio of 3:1. 3.2. Effect of Catalyst Loading. The effect of resin catalyst loading on the esterification rate over the range of 0-5 wt % of total solution mass was studied. The absolute initial rate of acid conversion was observed to increase linearly with catalyst loading (Figure 2). From this result, a turnover frequency (TOF) of 0.06 s-1 was determined for Amberlyst 15 resin at 80 C. Because lactic acid esterification is autocatalytic, a nonzero intercept was observed in Figure 2. For the 88 wt % lactic acid solution, this uncatalyzed esterification rate contributed 20% of the rate observed for 1% catalyst loading, a contribution that is equivalent to 0.2 wt % resin catalyst. This contribution is smaller for lower acid concentrations and is relatively unimportant for higher catalyst loadings; thus, it is omitted from the kinetic model described below. The effect of catalyst loading

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Figure 2. Initial rate of acid conversion versus catalyst loading. Reaction conditions: 88 wt % lactic acid solution, ethanol:lactic acid molar ratio ) 3, agitation rate ) 740 rpm, and reaction temperature ) 80 C. Figure 4. Esterification of 88 wt % lactic acid solution. Reaction conditions: ethanol:lactic acid molar ratio ) 3, catalyst loading ) 3 wt %, agitation rate ) 740 rpm, and reaction temperature ) 80 C. Legend: ([) L1, (2) L1E, (+) water, (*) ethanol, (9) L2, () L2E, (b) L3, and (0) L3E.

Figure 3. Arrhenius plot of rate constants from initial rate of lactic acid esterification. Reaction conditions: 88 wt % lactic acid solution, ethanol: lactic acid molar ratio ) 3, catalyst loading ) 3 wt %, and agitation rate ) 740 rpm. Legend: ([) k1, (9) k2, and (2) k3.

was also observed on reactions of oligomers such as L2E: when loading was increased from 0 wt % to 5 wt %, the rates of formation and hydrolysis of L2E were observed to increase proportionally. Most reactions were performed with a catalyst loading of 3 wt % or 0.03 kg catalyst/kg solution. 3.3. Effect of Reaction Temperature. The influence of the reaction temperature on the esterification rate was studied over the range of 62-90 C. An Arrhenius plot for the initial rate of reactions 1-3 is given in Figure 3. The activation energy for

Figure 5. Esterification of 50 wt % lactic acid solution. Reaction conditions: ethanol:lactic acid molar ratio ) 3, catalyst loading ) 3 wt %, agitation rate ) 740 rpm, and reaction temperature ) 80 C. Legend: ([) L1, (2) L1E, (9) L2, () L2E, (*) water, and (b) ethanol.

the esterification reactions (reactions 1-3), based on the initial rate, increased with the degree of oligomerization of lactic

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pletely described by reactions 1, 2, and 4 and by reaction 1, respectively.

L1 + EtOH yk /K z L1E + H2O \

1 1

k1

(1)

L2 + EtOH yk /K z L2E + H2O \

2 2

k2

(2)

L3 + EtOH yk /K z L3E + H2O \

3 3

k3

(3)

\ L2 + H2O yk /K z 2L1
4 4

k4

(4)

L3 + H2O yk /K z L1 + L2 \
5 5

k5

(5)

Figure 6. Esterification of 20 wt % lactic acid solution. Reaction conditions: ethanol:lactic acid molar ratio ) 3, catalyst loading ) 3 wt %, agitation rate ) 740 rpm, and reaction temperature ) 80 C. Legend: ([) L1, (2) L1E, (9) ethanol, and () water.

4.2. Evaluation of Mass-Transfer Limitations. Two possible modes of mass-transfer limitations are associated with heterogeneously catalyzed reactions: one across the solid/liquid interface (external mass transfer) and other within the catalyst particle (intraparticle diffusion). In the evaluations below, liquidphase effective diffusivities were calculated using the WilkeChang equation.19 Chakrabarti and Sharma20 suggested that external masstransfer limitations for ion-exchange resin-catalyzed reactions can be eliminated by conducting experiments at stirring rates of >500 rpm. To check their assumption, a theoretical calculation was performed to ascertain the magnitude of the external mass-transfer rate. Solid-liquid mass-transfer coefficients were calculated using a Sherwood number (kSL,jLt/De,j) of 2.0, which is the theoretical minimum value. The observed reaction rates of L1, L2, and L3 + L4 were calculated from their concentrationversus-time profiles. (Oligomers L3 and L4 were lumped together because of uncertainty in the response factor for L4 and because of its low concentration.) For each component, the maximum mass-transfer rate (kSL,j Cj) was determined to be at least an order of magnitude greater than the observed reaction rate, indicating that there are no significant solid-liquid mass-transfer limitations. Resin particles physically disintegrate at stirring rates of >800 rpm; therefore, all reactions were conducted at a speed of 740 rpm. The possible presence of intraparticle mass-transfer resistances was examined by determining the observable modulus (2 ) (-rj)Lt2/Cj/De,j) and applying the Weisz-Prater criterion; the maximum value of 2 observed was 0.15, which is sufficiently small to indicate that intraparticle mass-transport resistances are unimportant. This is consistent with previous reports that intraparticle diffusion limitations in reactions with Amberlyst15 under similar conditions could be considered negligible.9,10,21 4.3. Kinetic Model Equations. A simple nth-order reversible reaction model has been chosen to describe lactic acid esterification that has been catalyzed by Amberlyst 15 ion-exchange resin. The rate of formation for each component in the reaction

acids: from 48 000 kJ/kmol for esterification of monomer lactic acid (L1) to 74 100 kJ/kmol for esterification of trimer lactic acid (L3). These values are consistent with kinetically controlled reactions. Further reactions were performed at 80 C, which is the normal boiling point of ethanol. 3.4. Effect of Lactic Acid Feed Composition. Component profiles for esterification of 88, 50, and 20 wt % lactic acid feed solutions, under typical conditions, are given in Figures 4-6. Because of the presence of oligomers, it is apparent that predicting the behavior of the 88 wt % lactic acid solution requires a more-complex model than that required for 50 wt % and 20 wt % feed solutions.

4. Kinetic Model 4.1. Reaction Pathways. Based on the reactant and product composition profiles during esterification of the 88 wt % lactic acid solution, a set of reaction pathways have been defined for the kinetic model. The set of reactions, which are given in reactions 1-5 below, describes lactic acid monomer esterification as well as oligomer formation and esterification. All oligomers that are larger than dimers (L2 and L2E) are lumped together as L3 and L3E; the quantities of larger oligomers are small enough that they do not significantly influence the reaction, either kinetically or with regard to overall acid concentration and mass balances. A similar set of reaction pathways was proposed by Tanaka et al.14 Esterification of the 50 wt % and 20 wt % lactic acid solutions is com-

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system described by reactions 1-5 above is given in eqs 6-13 below.

Table 2. Parameters of the Kinetic Model parameter k0 1 k0 2 k0 3 k0 4 k0 5 value 1.91 105 kgsol/kgcat/s 2.66 104 kgsol/kgcat/s 1.24 107 kgsol/kgcat/s 1.62 104 kgsol/kgcat/s 6.67 103 kgsol/kgcat/s 48000 kJ/kmol 54500 kJ/kmol 74100 kJ/kmol 52000 kJ/kmol 50800 kJ/kmol 2.4 0.6 0.3 5.0 5.0

dxL1 dt

) wcat k10 exp 0

wcat k4 exp -

[ ( )( [ ( )(
EA1 RT RT EA2 RT
0

xL1xEtOH -

xL1ExW K1

EA4 xL12 K4

k50 exp dxL2 dt

( )(
RT

- xL2xW + - xL3xW

)] )] )]

EA5 xL1xL2 K5

)] )]

(6)

EA1 EA2 EA3 EA4 EA5 K1 K2 K3 K4 K5

) wcat k20 exp -

wcat k4 exp -

[ ( )( [ ( )(
E A4 RT

xL2xEtOH -

xL2ExW K2 K4 K5 xL12

k50 exp dxL3 dt

( )(
RT E A5 RT

xL2xW -

+ - xL3xW

EA5 xL1xL2

(7)

) wcat k30 exp -

[ ( )(
EA3 RT

wcat k50 exp -

[ ( )(
E A1 RT

xL3xEtOH -

xL3ExW K3

xL3xW -

xL1xL2 K5

)]

(8)

dxL1E dt

) wcat k10 exp -

[ ( )(
E A2 RT E A3 RT

xL1xEtOH -

xL1ExW K1

)]

(9)

dxL2E dt dxL3E dt

) wcat k20 exp -

) wcat k30 exp -

E A1 xL1ExW dxEtOH ) wcat k10 exp xL1xEtOH + dt RT K1 E A2 xL2ExW xL2xEtOH + wcat k20 exp RT K2 E A3 xL3ExW k30 exp xL3xEtOH (12) RT K3

[ ( [ ( [ ( [ (

)( ( )(
K2

)( )( )(

xL2xEtOH xL3xEtOH -

xL2ExW K2

xL3ExW K3

)] )] )]

(10)

The equilibrium constant for L1E formation (K1) was obtained via the reaction of 20 wt % solution of lactic acid with ethanol in the presence of Amberlyst 15. Complete chemical equilibrium was achieved after 72 h of reaction. The value for K1 was determined to be 2.4. The equilibrium constants for hydrolysis of all linear acid oligomers were taken as 5.0, based on our earlier work.3 The equilibrium constants for L2E and L3E formation via esterification of L2 and L3 were treated as adjustable parameters in the model. The pre-exponential factors (k0) and activation energies i (EAi) in the kinetic model were fit to the experimental data. To minimize the number of degrees of freedom, the activation energies for reactions 1-3 were fixed at the values obtained from Figure 2 for initial reaction rates. Values for the five preexponential factors and EA4 and EA5 were then generated by nonlinear regression analysis using MATLAB 7.0 to minimize the sum of the mean-square differences (eq 14) between experimental and predicted liquid-phase mole fractions for all species over the course of reaction. The resulting pre-exponential factors, activation energies, and equilibrium constants for all reactions are given in Table 2.

(11)
5. Discussion

Fmin2 )

(xi,cal - xi,expt)2 samples

nsamples (14)

)]

EA1 xL1ExW dxW - xL1xEtOH ) wcat k10 exp dt RT K1 wcat k20 exp k30 exp EA2 xL2ExW RT

( )(
RT

[ ( )( [ ( )(
K3 K4 xL12

EA3 xL3ExW

xL2xW -

- xL3xEtOH

+ k50 exp -

)] [ ( ) ( )( )]
+ wcat k40 exp xL3xW + xL1xL2 K5 E A4 RT E A5 RT

- xL2xEtOH +

)] )

(13)

To illustrate the validity of the kinetic model, composition profiles were generated from eqs 6-13 for the entire range of experimental conditions examined. Representative results of the model are shown in Figures 1-6. (Additional esterification results are given in the Supporting Information.) For 50 and 88 wt % lactic acid, predictions for component profiles were in reasonably good agreement with the experimental values; for 20 wt % lactic acid, predictions were in excellent agreement with experiments. Error values or deviations (expressed as a percentage) between experimental and model predictions for each component are provided in Table 3. For experiments with 88 wt % feed solution, errors were small during the initial 180 min of reaction but became larger as the reaction approached equilibrium. Errors were larger for L2E and L3E on a percentage basis, but those species were present in small quantities and, thus, do not significantly affect major component concentrations. For 88 wt % lactic acid, overprediction of L2E formation at equilibrium resulted in overprediction of acid conversion relative to the experiment (Figure 3). The kinetic model described here is based on the concentration of species (e.g., mole fraction) in solution. We recognize

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Table 3. Comparison of Experimental Values and Model Prediction for Esterification of 20, 50, and 88 wt % Lactic Acid Aqueous Solutions with Ethanol EtOH:LA molar ratioa 1 2 3 4 3 3 3 3 3 3 3 1 2 3 4 3 3 3 3 3 3 1 2 3 4 3 3 3 3 3 3
a

catalyst loading (wt %) 3 3 3 3 1 2 4 5 3 3 3 3 3 3 3 1 2 4 3 3 3 3 3 3 3 1 2 4 3 3 3

reaction temperature (C) 80 80 80 80 80 80 80 80 62 72 90 80 80 80 80 80 80 80 61 71 90 80 80 80 80 80 80 80 60 70 90

L1

L2

L3

Percent Error L1E L2E 20.5 10.1 7.7 2.7 11.2 7 3.6 2.6 2.5 0.6 6.6 20.2 11.2 4.8 5 13 4 3.5 14.2 5.2 4.1 9.2 3.5 4.2 17 9.7 5.8 14.1 2.8 5.6 4.6 37.1 15.9 12.2 16.9 16 9 5.7 6.6 9.6 3.6 14.5 49 29.2 37.1 25.9 14.7 24.4 24.7 39.1 14.8 34.8

L3E 25.1 28 20.5 25 31.2 29.8 29.1 16 31.5 13.1 29.6

EtOH 10.9 4.4 2 1.1 1.6 1.4 1.4 1.2 0.8 0.6 3 6.2 2.9 1.1 0.5 2.0 1 1.4 0.4 1.2 1.2 0.8 0.3 0.2 0.1 1.3 0.2 0.7 0.2 0.5 0.2

W 5.2 2.3 2.1 0.9 2.1 1.6 1 0.6 0.8 0.2 4.2 0.4 0.04 0.4 0.6 0.2 0.4 0.4 0.8 0.6 0.5 0.06 0.05 0.07 0.2 0.4 0.03 0.2 0.08 0.2 0.05

88 wt % Lactic Acid Solution 8.7 19.9 24 8.9 17.2 15.5 13.9 15.8 11.2 22.2 21 12.8 11.3 9.8 9.3 7.4 10.1 7.6 15.7 7 4.8 11.5 33.4 27.9 8.3 1.2 1.8 5.5 3.5 3.2 9.5 41.8 25.9 50 wt % Lactic Acid Solution 2.6 6.9 2.2 5.1 5.1 10.3 8.4 20.4 4.2 1.8 5.6 6 6.3 14 6.6 3.2 7.1 8.4 1 20.8 20 wt % Lactic Acid Solution 1.5 1.4 1.8 4.4 5.8 1 2 1.2 2.5 1.2

Molar ratio of ethanol to lactic acid.

that species activity is a fundamentally more appropriate variable for kinetic modeling; however, for this system, there is little or no experimental data available on liquid-phase activity coefficients of lactic acid, its oligomers, and their esters in ethanolwater solutions. Prediction of such activity coefficients, which is possible using UNIFAC or other group contribution methods, is subject to substantial uncertainties, particularly for the high concentrations that have been examined here. In fact, we did prepare an activity-based kinetic model for the lactate esterification system that included the application of UNIFAC for activity coefficient prediction. The optimized activity-based model gave errors larger than those obtained with the mole fraction-based model; thus, we do not believe there is any advantage to application of such a model at this time. The choice of simple nth-order kinetic expressions for esterification, as opposed to a more mechanistically based approach (such as a Langmuir-Hinshelwood model), was made partially because of uncertainty in the liquid-phase environment within the Amberlyst 15 cation-exchange resin. When placed into aqueous solutions that contain ethanol and organic acid, Amberlyst 15 swells, because of the selective absorption of water.22 We observe the same behavior with dilute solutions of lactic acid (20 wt % and 50 wt %) in esterification, where water is present in large excess, relative to lactic acid (20-fold excess for 20 wt % and 6-fold excess for 50 wt %), and, thus, free water can absorb. When concentrated (88 wt %) lactic acid, where the molar ratio of water to lactic acid is 0.7, is subject to esterification, ethanol rather than water is preferentially absorbed into Amberlyst 15. We attribute this behavior to the association of free water with lactic acid, such that very little or no free

water is available for absorption onto resin particles at high lactic acid concentration. This hypothesis was further verified by an experiment in which a known composition of 88 wt % lactic acid and ethanol was brought in contact with the resin at room temperature, equilibrated for 30 min, and analyzed. At this temperature, no reaction was observed and ethanol was observed to be preferentially adsorbed. 6. Conclusions The kinetics of esterification of lactic acid and its linear oligomers with ethanol have been described using simple nthorder reversible rate expressions. Pre-exponential factors, activation energies, and equilibrium constants were either fit to the experimental data using nonlinear regression analysis or, in some cases, were calculated directly or taken from other work. Activation energies in the range of 48 000-74 100 kJ/kmol and analysis of mass-transport resistances indicate that the reaction is kinetically controlled. The predicted time-dependent species profiles in esterification were in good agreement with experimental results over a wide range of reaction conditions. Acknowledgment Financial support from National Corn Growers Association and the U.S. Department of Energy are greatly appreciated. The authors also appreciate assistance from MSCRTSF at Michigan State University for mass spectroscopic analysis and identification of various components. Supporting Information Available: Figures containing experimental data and model fit for additional lactic acid

Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006 5257

esterification studies (PDF, 28 pages). This material is available free of charge via the Internet at http://pubs.acs.org. Nomenclature and Units Cj ) concentration of species j in liquid-phase solution (gmol/kgsoln) De,j ) effective diffusivity of species j in resin (m2/s) EAi ) energy of activation for the ith reaction (kJ/kmol) ki0 ) pre-exponential factor for the ith reaction (kgsol/kgcat/s) kSL,j ) mass-transfer coefficient of species j (m/s) Ki ) equilibrium constant for the ith reaction Lt ) resin particle size equivalent; Lt ) D/6 ) 1 10-4 m R ) gas constant; R ) 8.31 kJ/(kmol K) rj ) initial reaction rate of species j (g-mol/kgsoln/s) T ) temperature (K) wcat ) catalyst concentration (kgcat/kgsoln) xj ) mole fraction of species j in liquid-phase solution Greek Letters 2 ) observable modulus Literature Cited
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ReceiVed for reView December 6, 2005 ReVised manuscript receiVed April 18, 2006 Accepted May 10, 2006 IE0513604