20th European Symposium on Computer Aided Process Engineering ESCAPE20 S. Pierucci and G.

. Buzzi Ferraris (Editors) 2010 Elsevier B.V. All rights reserved.

Optimization of Batch Reactive Distillation Process: Production of Lactic Acid

Elmahboub A. Edredera, Iqbal M. Mujtabaa, Mansour Emtirb
a

School of Engineering, Design and Technology, University of Bradford, West Yorkshire, BD7 1DP,UK. Email: I.M.Mujtaba@bradford.ac.uk bNational Oil Corporation, P.O. Box 2655, Tripoli, Libyan Arab Jamahiriya

Abstract
Lactic acid is widely used as a raw material for the production of biodegradable polymers, food, chemical and pharmaceutical industries. The global market for lactic acid is set to reach 259 thousand metric tons by year 2012. In this work, the performance of batch reactive distillation is evaluated to produce lactic acid by hydrolysis reaction of methyl lactate. Minimum time optimisation problem is developed incorporating a process model within gPROMS software for range lactic acid purity (from 80 % to 99 %) and the amount of product. For a given column the minimum operation time configuration is obtained by optimising the reflux ratio profile. The lactic acid being heaviest in the reaction mixture, reflux ratio policy plays an important role in removing the light product methanol from the system while ensuring the presence of both reactants in the reaction zone to maximise the conversion to lactic acid. Also unlike esterification reaction, total reflux operation is demanded at the end of the operation in the hydrolysis reaction to purify lactic acid to about 99 % by removing the remaining reactants from the reboiler. Keywords: Batch reactive distillation, Hydrolysis, Lactic acid, Methyl lactate, Optimization.

1. Introduction
Several researchers in the past have proposed the esterification of lactic acid (impure) with methanol to obtain lactate ester which is then separated by distillation. The distilled lactate ester is then hydrolyzed into pure lactic acid (Fig. 1). Both continuous (Li et al., 2005; Kumar et al., 2006 b and Rahman et al., 2008) and batch (Choi and Hong, 1999; Kim et al., 2000; Kim et al., 2002 and Kumar et al., 2006 a) have been employed for the recovery of lactic acid. Li et al. (2005) studied purification of lactic acid based on the esterification of diluted lactic acid with methanol in a reactor followed by hydrolysis of methyl lactate in continuous column to achieve pure lactic acid. They observed the presence of methyl lactate in the distillate due to incomplete hydrolysis to lactic acid. Kumar et al. (2006 a) considered both experiments and simulation of a continuous reactive distillation process coupling esterification of lactic acid and hydrolysis of methyl lactate to obtain pure lactic acid. They observed 100 % conversion in a column of 20 stages. Rahman et al. (2008) applied Differential Evolution (DE) algorithm for the optimisation of CSTR reactor followed by distillation column with hydrolysis of methyl lactate. The objective was to minimise the overall cost which gives the optimal variables such as: esterification reaction temperature, number of stages, feed location, reflux ratio, catalyst weight, and number and position of reactive stages.

Edreder et al. Choi and Hong (1999) investigated an apparatus (two reactors and two batch distillation columns) to carry out the esterification and hydrolysis reactions and achieved relatively pure lactic acid. Kim et al. (2000) considered a batch reactive distillation with esterfication and hydrolysis for the recovery of lactic acid using experiments and simple modelling to obtain optimum design and effective operation. Kim et al. (2002) analyzed the dynamic behaviour of batch reactive distillation of lactic acid in terms of instantaneous rate of esterification reaction. They observed that the rate increased by controlling of boil up rate and residence time during the operation by changing both the methanol recycle stream and feeding mode. They also compared semi-batch operation with the batch mode. It was found that continuous feeding of methanol enhanced the recovery of lactic acid. Kumar et al. (2006 b) explored and investigated a novel reactive distillation strategy involving experimental esterification and hydrolysis reaction for recovery of lactic acid. They studied the effect of operating parameters such as feed concentration, mole ratio, catalyst load, and boil up-rate on the recovery of lactic acid. As seen from the previous researches that the most of the work has been focused on experiments to recover lactic acid. Optimisation problem in terms of minimum batch time for hydrolysis of methyl lactate to lactic acid has not been considered in the past. Therefore, in this work, the performance of batch reactive distillation in terms of minimum batch time is considered with the hydrolysis reaction of methyl lactate. A dynamic model for the process (Edreder et al., 2009) is used which is incorporated into the optimization framework. Product amount and purity are used as constraints. Reflux ratio is used as control variable which is discretised using Control Vector Parameterization technique. This results in a Non Linear Programming (NLP) problem, which is solved using an SQP-based optimization technique available within gPROMS (2004).

Esterfication MeOH (Unreacted) H2O ML

Hydrolysis MeOH H2O

LA + MeOH Make up H2O Hydrolysis Methyl lactate (ML) + Water (H2O) Esterification

LA (Final product)

Lactic acid (LA) + Methanol (MeOH)

Fig. 1 Batch reactive distillation process for lactic acid synthesis

Optimization of Batch Reactive Distillation Process: Production of Lactic Acid

2. Hydrolysis Reaction
2.1. Chemical Reaction and Kinetics The hydrolysis reaction of methyl lactate can be expressed as follows Methyl lactate (1) + Water (2) <=> Lactic acid (3) + Methanol (4) (1)

B.P (K) 417.15 373.15 490.15 337.15 A quasi-homogeneneous (QH) activity (ai = i xi) based kinetic model is used (taken from Sanz et al., 2004) and can be written as:

r = 1 . 65 10 5 exp(

50 . 91 48 . 52 )a 3 a 4 ) a 1 a 2 1 . 16 10 6 exp( RT RT

(2)

2.2. Vapor-Liquid Equilibrium (VLE) K-values (VLE constants) are computed from (Eq. 3) where i is computed from UNIQUAC equation, the vapor pressure (Psat) of pure components has been obtained by using Antoines equation. The UNIQUAC binary interaction parameters and Antoine parameters were taken from Sanz et al. (2003). Vapor phase enthalpies are calculated using empirical equations from formulation Holland (1981) and the liquid phase enthalpies were calculated by subtracting heat of vaporization from the vapor enthalpies
K = i Pi sat / P

(3)

3. Optimization Problem
The performance of batch reactive distillation column is evaluated in terms of minimizing the operating time. Single and multiple reflux ratio strategies are used, yielding an optimal reflux ratio policy. For multiple reflux ratio policy, within each interval the reflux ratio (assumed piecewise) together with the switching time from one to other interval is optimized. Values of profile over time intervals concerned are assumed. The amount of bottom product (lactic acid) and product purity are specified as constraints bounds in the optimization problem. In addition to the constraints mentioned the differential algebraic equations (DAE) process model act as equality constraints to the optimization problem.
given: determine: so as to minimise: subject to:

the column configuration, the feed mixture, vapour boilup rate, product purity, amount of bottom product. optimal reflux ratio which governs the operation the operation time. equality and inequality constraints (e.g. model equations).

Mathematically, the Optimisation Problem (OP) can be represented as:

Min R (t) s.t

tf
(4)

Pr ocess Model Equation B = B* + x 3 x* 3

(equality constriants) (inequality constraint) (inequality constraint)

Edreder et al.

Where B, x3 are the amount of bottom product and composition at the final time tf, (denotes that the B and x3 are specified), R(t) is the reflux ratio profile which is optimized. is the small positive number of the order of 10-3.

4. Case Study
4.1. Specifications The case study is carried out in a 10 stages column (including condenser and reboiler) with condenser vapour load of 2.5 (kmol/hr). The total column holdup is 4 % of the initial feed (50 % is taken as the condenser hold up and the rest is equally divided in the plates) and the reboiler capacity is 5 kmol. The feed composition <Methyl Lactate (1), Water (2), Lactic acid (3), Methanol (4)> is : <0.5, 0.5, 0.0, 0.0>. 4.2. Results and Discussions Here, four cases are studied. In Case 1, single time interval (NCI = 1) is used while in the other three cases, time dependent reflux polices (discretised into two (NCI = 2), three (NCI = 3) and four (NCI= 4) time intervals) are considered. For each case, Table 1 summarises the optimisation results in terms of optimal reflux ratios, conversion of methyl lactate to lactic acid and minimum operating time for different product purity by using single and time dependent reflux policies.

Table 1 Summary of the results using single and multiple reflux ratio strategies Case 1: NCI=1 interval
x purity R tf (hr) Conv.% x purity

Case 2: NCI= 2 intervals

t1,R1 R 2, t f Conv. %

0.80 0.85 0.90 0.925 0.950 x purity 0.800 0.850 0.900 0.925 0.950 0.975 0.990 x purity 0.800 0.850 0.900 0.925 0.950 0.975 0.990

0.933 0.957 0.973 0.993 *

14.88 23.28 46.04 135.4 * t1,R1 2.33, 0.813 7.49, 0.907 4.86, 0.886 5.75, 0.899 6.24, 0.909 16.31, 0.956 *

77.7 82.5 86.9 89.2 *

0.80 0.85 0.90 0.925 0.950

9.54, 0.914 9.43, 0.937 8.66, 0.922 12.50, 0.950 10.55, 0.935

0.957, 13.72 0.957, 19.04 0.979, 23.95 0.983, 31.41 0.990, 44.73

77.7 82.7 87.9 90.1 92.5 Conv. % 77.8 82.9 88.1 90.5 92.9 94.8 * Conv. % 77.9 82.9 88.3 90.7 93.3 94.7 96.0

Case 3: NCI= 3 intervals

t2,R2 2.00, 0.907 3.99, 0.971 3.74, 0.950 12.08, 0.975 11.09, 0.975 17.70, 0.988 * t3,R3 2.63, 0.918 5.10, 0.962 3.88, 0.937 4.61, 0.924 8.79, 0.964 17.43, 0.988 51.10, 0.996 R3 , t f 0.945, 11.27 0.964, 16.72 0.980, 21.90 0.989, 28.88 0.992, 37.82 0.996, 55.07 * R4 , t f 0.935, 10.80 0.957, 16.55 0.976, 20.09 0.982, 27.26 0.989, 34.17 0.996, 54.88 1.00, 142.08

Case 4: NCI= 4 intervals

t1,R1 0.500, 1.00 1.280, 0.921 0.420, 1.00 0.500, 1.00 0.540, 1.00 6.03, 0.962 15.34, 0.954 t2,R2 2.11, 0.800 5.49, 0.908 2.70, 0.835 1.26, 0.779 2.93, 0.848 10.95, 0.955 20.72, 0.994

Note: * means Not possible to achieve the product at the desired purity

It is noticed from the optimization results that, the column operated with single time interval for reflux ratio was not sufficient to produce the main product at high purity specifications (> 0.925 mole fraction a lactic and in the bottom product). The multi-

Optimization of Batch Reactive Distillation Process: Production of Lactic Acid

reflux interval strategies (Case 2-4) were found to be better to produce products with higher purity specifications with shorter batch time. Fig. 2 proves this fact in terms of minimum operating time as a function of bottom product purity specifications and reflux ratio policy. For example the operation time using two time intervals (in case of product purity 0.925) is reduced by 76.8 % compared to that obtained by using single interval. This is due to the fact that the column initially operated at lower reflux ratio (R1) to remove the light component (methanol) and then at higher reflux (R2) to meet the product specification in a shorter time. Note, it was not possible to achieve the bottom product at (0.975 purity) with two reflux intervals. Observation also shows that the operating time for some cases can be saved by 79 % when the column operated using 3 reflux ratio intervals compared to the operation times obtained using single interval. Moreover the operating time has been saved by an average of 37 %, 46 % and 48 % using 2, 3 and 4 time intervals respectively for the purity range from 0.8 to 0.925. This clearly shows the benefit of using multi reflux intervals. It can be observed also that at product purity 0.975 no significant improvement is noticed in terms of operating time when the column operates with 3 or 4 reflux ratio level intervals. The lactic acid product with purity of 0.99 molefraction was not possible to achieve with 3 reflux intervals but was possible to achieve with 4 reflux intervals. Note, in the last time interval (R4, tf) for Case 4, the column operates at total reflux for a long period (~ 91 hrs). Although there was no distillate withdrawn during that period, composition profiles in the condenser holdup tank, internal stages and in the reboiler took place to purify the bottom product to the desired purity. Finally, note for each product purity, the amount of bottom product could be further improved by multi-reflux policy. Unlike esterification reaction in conventional batch reactive distillation where the reaction product (ester) is the lightest, the hydrolysis reaction considered here produces the product (lactic acid) which is the heaviest in the mixture. The column has to always operate at high reflux ratio so that both the reactants are available in the reaction zone (reboiler and stages). Low reflux ratio operation will separate the reactants from the system and will thus lower the conversion (as can be seen in Case 1). Multi-reflux operation enjoys more freedom to balance between the conversion and product purity (as can be seen in Cases 2-4)

Fig.2. Minimum batch time as a function of lactic acid purity specification

Edreder et al.

5. Conclusions
The performance of batch reactive distillation process in terms of minimum batch time is studied here with hydrolysis reaction of methyl lactate to produce lactic acid and methanol. A dynamic optimization problem incorporating a process model is formulated to minimize the batch time subject to constraints on the amount and purity of lactic acid. Piecewise constant reflux ratio profile (with single and multiple time intervals) is considered as a control variable. A series of minimum time problems was solved at different values of product purity ranging from 0.8 to 0.99 molefraction and the impact of time dependant reflux ratio policy on the product quality and batch time are analyzed. For a given column configuration, it is noticed that, the column operated with single reflux ratio interval was not sufficient to produce high purity lactic acid. The saving in operating time and improvements in product purity shows the benefit of using multireflux intervals strategy rather than single reflux ratio policy. Multi-reflux operation enjoys additional freedom to have the balance between the conversion and the product purity.

References
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