Project Synopsis

On
“Modelling and Simulation of Continuous Reactive
Distillation”
Submitted By
Mr. Mayurkumar P. Patil.
(2nd yr. M. Tech. Chem. Engg.)
Guided By

Prof. Dr. J. B. Naik Dr. Imran Rahman

Head (Chem. Engg.) Principal Scientist,
UICT, NMU, Jalgaon CEPD, NCL, Pune

University Institute of Chemical Technology,

North Maharashtra University,
Jalgaon-425001.(MS)
 Contents
 Introduction
 Basics Of Reactive Distillation
 Production Of Ethyl Acetate
 Non Ideal Vapor Liquid Equilibrium
 Reaction And Reaction Kinetics
 Mathematical Model Of The Reactive Distillation
 Flow Chart Of Simulation Program For Continuous Reactive
Distillation
 Column Specifications And Other Parameters
 Result And Conclusion
 Experimental Setup And Procedure
 Future Work
 References
 Introduction
 Distillation is one of the most important separation processes in chemical industry.

 The reactive distillation provides an attractive alternative for reaction/separation

processes with reversible reactions, especially for etherification and esterification.

 The main advantage of using reactive distillation is the reduction of capital and
operating costs.

 The dynamic behavior of process is difficult to study.

 Modelling and will simulate of a continuous reactive distillation column for the
production of ethyl acetate from acetic acid and ethyl alcohol using MATlab and
compare the simulation results for ethyl acetate purity with experimental data for a
given reaction system in the distillate and in the bottoms.
 Basics Of Reactive Distillation
 Reactive distillation is attractive in chemical and phase equilibrium
systems. It can be either equilibrium reactions or non-equilibrium
(irreversible) reactions.

Fig.1- Ideal reactive distillation column

Commercial applications of Reactive Distillation
 Esterification of acetic acid with ethanol to produce Ethyl acetate and
water.
 Reaction of formaldehyde and methanol to produce methylal and water,
using a solid acid catalyst.

Advantages of Reactive Distillation-

 Improved selectivity, conversion and product quality

 Less waste and fewer byproducts.

 Increased speed and improved efficiency.

 Use of heat of reaction to reduce energy consumption through energy

integration.
 Production Of Ethyl Acetate
 Ethyl acetate is produced by the esterification reaction of ethyl alcohol
and acetic acid using catalysts.
CH3COOH + C2H5-OH CH3COOC2H5 + H2O

 Main problems encountered in achieving high purity in ethyl acetate

• Unfavorable reactant conversion;
• Similar K-values of ethanol, water, and ethyl acetate;
• Temperature profile in the column;

 Uses of ethyl acetate-

 Surface coating and thinners
 Pharmaceuticals
 Flavors and essences
 Flexible packaging
 Non Ideal Vapor Liquid Equilibrium
 For non-ideal mixture or azeotropic mixture additional
variable γi,

 1 = γi, …… For ideal mixture

 1 ≠ γi……… For non-ideal mixture

Calculation of Activity Coefficient(γi,)-

Universal Quasichemical (UNIQUAC) Activity Coefficient Model:-
Table 1. UNIQUAC Model Parameters
 Estimation Of Model Parameters:
 Equilibrium relations-
The modified of Raoults law it is,

where,

 Antoine Model-
The Antoine equation is derived from the Clausius –Clapeyron relation,

Table 2- Antoine Constants for components

 Bubble point calculation-
To estimate the bubble point by Newton Raphson's iterative method
the equation is written in the form,

where,

 Enthalpy Estimation-
Enthalpy is a measure of the total energy of a thermodynamic system.
It is a function of temperature at the operating pressure of the column.
 Reaction And Reaction Kinetics
 Reaction:

 Reaction Kinetics:-
second order reversible esterification reaction,

Table.3-Arrhenius equation parameters

and are the pre-exponential factor
and are the apparent activation energy in
R is gas constant in
 Mathematical Model Of The Reactive
Distillation
Assumptions used in model development:
1. Each stage is a perfectly mixed.
2. The vapor and liquid leaving any stage are in physical equilibrium.
3. Vapor molar holdup and vapor-phase chemical reactions were
neglected.
4. Constant vapor flow in the column.
5. Constant liquid flow at each section.
6. Constant total molar hold-up at each stage for Liquid.
Fig.2-Configuration for reactive-distillation column
 The dynamic Total, Component balances for the column are-
For Condenser and reflux drum-

For Rectifying and stripping trays-

For Reactive trays-

For Feed trays-

For Reboiler and Column Base-

These ordinary differential equations solved using the ode23s command of

MATLAB R2011b
Flow Chart Of Simulation Program For Continuous Reactive
Distillation

Fig.3- Algorithm For Continuous Reactive Distillation

 Column Specifications And Other Parameters

Table 4- Specification of the reactive distillation column and feed conditions

 Result And Conclusion
1

Ethanol
Liq. Mole Fraction in Bottom

0.8 Ethyl Acetate

Acetic acid

0.6 Water

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Time in min.
0.9

0.8
Liq. Mole Fraction in Distillate

0.7 Ethanol

0.6 Ethyl acetate

0.5 Acetic acid

Water
0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Time in min.

Fig.4- Liquid composition profile in bottom and distillate

 Comp. Distillate(Simulated) Reboiler (Simulated)

Ethanol 0.1029 0.4794

Ethyl Acetate 0.8605 0.2089

Acetic acid 0.0011 0.1874

Water 0.0353 0.1241

Table.5-At Reflux ratio=10 Unsteady State Simulated Composition Values

From the graph it is observed that the composition of ethyl acetate

purity increases in distillate and but concentration of ethyl acetate in
bottom is increases continuously which is unfavorable for the
modeling and simulation. The maximum concentration of liquid ethyl
acetate in distillate is 0.86. The UNIQUAC model and Bubble point
calculation for liquid phase gives the actual values of activity
coefficients and boiling point of the components respectively.
 Conclusion
 The reactive distillation of ethyl acetate production (CH3COOC2H5),
using acetic acid (CH3COOH) and ethanol (C2H5OH), in a plate
column can be done using Matlab R2011b user interface version
7.13.0.564.

 The mathematical model developed has shown satisfactory results in

simulating a reactive distillation column for the esterification of
acetic acid with ethanol to produce ethyl acetate.

 Due to the complex interaction between of reactive distillation

column, design concepts require good modeling program. The
program which used in the present study show good validity.
 Experimental Setup And Procedure

Fig.5- Experimental set up for double feed flow diagram in

Continuous Reactive Distillation
 Future Work
 In future to carry out experimental procedures as described above.

 Compare the Simulated result with experimental values.

 To Study the effects of different parameters such as: catalyst weight,

reflux ratio, no. of stages and feed concentration on the performance of
reactive distillation.

 Analysis of product using various analytical instruments.

 Further, to simulate the same system for production of Ethyl Acetate by

another simulator like Aspen Plus 11.1 user interface.
 Attended International Conference & Expo on Latest Developments in
Vegetable Oil Processing “67th Annual Convention of Oil Technologists’
Asscociation of India” from Nov. 23-24, 2012 held at ITC Maratha, Mumbai

 Participated in the Poster Presentation entitled ‘Modelling & Simulation of

Catalytic Membrane Reactor in Water-Gas shift reaction’ in
‘Chemference’12 Organised by Chemical Engg. Department ICT-Mumbai &
IIT-Mumbai from 10 Dec. to 11 Dec.2012

 Paper Presentation in CHEMCON-2012 from Dec. 27-30, 2012 held at NIT

Jalandhar (Punjab) (International Conference on Energy & Environment in
process Industries IIChE) entitled-
1) KineticsTransesterification of Different Oils.
2) Downstream Recovery Of Furfural From Its Byproducts From Biomass.
3)Optimization of Liquid-liquid Extraction Column Using Differential
Evaluation Technique.
 References
 William L Luyben, Distillation design and control using ASPEN simulation, Wiley
interscience,(2006).
 William L Luyben, Cheng-Ching Yu, Reactive Distillation Design And Control, John
Wiley & Sons Publication, ISBN 978-0-470-22612-4(2008).
 William L Luyben, Process Modeling, Simulation and Control for Chemical Engineers
second edition. McGraw-Hill, Inc ISBN-0-07-100793-8(1990).
 Mujtaba I. M., Batch Distillation Design and Operation. Series On Chemical Engineering
Vol.3, Imperial College Press, ISBN 1-86094-437-X (2004).
 Rani A, Singh V., and Gupta J.R.P.,(2011) Simulation and Control of Distillation Process.
Journal Of Computing, Volume 3, Issue 7, July 2011, Issn 2151-9617.
 Huang Z., Tian H., Qiu T.,Wu Y., Simulation Studies of Reactive Distillation Processes for
Synthesis of Ethyl Acetate. IEEE 978-1-4244-5539-3/10(2010).
 Kawathekar R., Riggs J. B., Nonlinear model predictive control of a reactive distillation
column. Elsevier Ltd. Control Engineering Practice 15 (2007) 231–239.
 Bhatt K. and Patel N. M., Generalized Modeling and Simulation of Reactive Distillation:
Esterification Pelagia Research Library Advances in Applied Science Research,3
(3):1346-1352 (2012).
 Almila Bahar, Canan Ozgen, “Experimental and Modeling Studies for a Reactive Batch
Distillation Column”(2007).
 A.K.Jana‚ Chemical Process Modelling and Computer Simulation. Prentice-Hall of India
pvt. Ltd. ISBN-978-81-203-3196-9(2008).