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Design,Simulation and Control of a Methyl Acetate Reactive Distillation Column

using ASPEN Plus

Conference Paper · April 2015

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Modeling, Simulation and Control of Methyl Acetate Reactive Distillation System

Abhishek Ghosh

ID Number: 2012 A1PS362P

Department of Chemical Engineering

BITS Pilani, Pilani Campus

Submitted to:

Dr. H.K. Mohanta

In Completion towards

Course Code: CHE F376

Course Name: Design Project

Second Semester 2014-15

1
 Acknowledgements
I would like to express heartfelt gratitude to firstly, Prof. H.K.Mohanta, for his patient guidance
through the roadblocks that I faced while completing the project. He has also been an invaluable
source of research literature links that helped me frame the problem statement in much clearer
terms.

Mr. Subhajit Majumdar has also been instrumental in granting me access to the ASPEN Plus
software installed in the CAD laboratory.

Dr. Suresh Gupta is also thanked for his assistance in allotting the specified Design Project to
me.

Dr. Pradipta Chattopadhyay has been extremely accommodating in helping chart out a detailed
plan to schedule the evaluation components in a timely manner.

2
 Table of Contents
1. Process Intensification Using Reactive Distillation Columns………………………….…4
2. Introduction to the Reaction……………………………………………………………….4
3. Conditions for Reactive Distillation Processes……………………………………………5
4. Process Modeling……………………………………………………………………….…6
5. Possible Ranges of Reflux Ratios…………………………………………………………8
6. Simulation Results and Analysis…………………………………………………………8
7. System Nonlinearity : Input Multiplicity………………………………………………….9
8. Control Structures for Reactive Distillation…………………………………….……….10
9. Conclusion………………………………………………………………………….……14
10. Limitations of the Present Study and Future Scope……………………………….……..14
11. Appendix………………………………………………………………………………....15
12. References………………………………………………………………………………..17

Figures

1. Figure 1: Main Flow Sheet Design (Single Feed Modification of the Eastman Column)
2. Figure 2: Setting the Base Method to NRTL for Thermodynamic Calculations
3. Figure 3: Guidelines for Choosing Thermodynamic Property Methods in ASPEN
4. Figure 4: The optimum reflux ratio would lead to a minimum number of stages. Also,
from the diagram, the feasible range of reflux ratios decreases with increasing pressure.
(Huss Robert, Chen Fengrong .et.al)
5. Figure 5: Sensitivity Analysis of Mole Fraction Methyl Acetate in the Top Product and
Water in the Bottom Product as a Function of Molar Reflux Ratio
6. Figure 6: Control Structure 5
7. Figure 7: Introduction of a 20% increase in the Disturbance Variable (AcOH) and its
Effects on Different System Variables
8. Figure 8- Control Structure 7
9. Figure 9: Effect of a +20% change in the Reboiler Heat Duty on the Temperature of
Trays 3 and 15, the Feed Flow Rates and the Mole Fraction of Methyl Acetate in the Top
Product and of Water in the Bottoms

Tables
1. Table 1: Feed Condition……………………………………………………………….6
2. Table 2: Reactive Distillation Column Specifications……………………………...…6

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 1. Process Intensification Using Reactive Distillation Columns
1.1.The benefits of process intensification using reactive distillation are:
a. Increased yield, because of overcoming chemical and thermodynamic equilibrium
limitations
b. Improved selectivity by suppression of side reactions
c. Reduced energy consumption due to effective utilization of reaction heat, in case of
exothermic reactions
d. Avoidance of hot spots due to simultaneous liquid evaporation
e. Ability to separate close boiling point components
1
Methyl acetate, produced in the subsequent chemical reactions, is denoted chemically as
MeOAc. It is a carboxylate ester with the formula CH3COCH3 is a flammable liquid with
a characteristically pleasant smell, reminiscent of some glues and nail polish removers.
Methyl acetate is occasionally used as a solvent, being weakly polar and lipophilic.
Methyl acetate has a solubility of 25% in water at room temperature. Methyl acetate is
not stable in the presence of strong aqueous bases or aqueous acids.

2. Introduction to the Reaction

Methyl acetate can be made using the liquid-phase reaction of acetic acid and methanol in
the presence of an acid catalyst. (e.g. sulphuric acid or sulphonic acid ion exchange resin)
at a pressure of 1 atm.

HOAc + MeOH <--> MeOAc + H2O

2
Since the high polarity of water and methanol compared to methyl acetate leads to
strongly non-ideal solution behavior, an activity-based rate model for the reaction
chemistry was developed by Song, Venimadhavan, Manning, Malone and Doherty
(1998). It utilizes the Hinshelwood/Hougen-Watson isotherm.
[Mcat K1 {a MeOH * a HOAc – (a MeOAc * a H20) / keq}]
------------------------------------------------------------------------------------------
(1 + KHOAc aHOAc+KMeOHaMeOH+KMeOAcaMeOAc+KH20aH20)2

Here the reaction equilibrium constant and the forward rate constant are given by:

k eq = 2.32 exp (782.98 / T)

K1 = 6.942x109 exp(-6287.7 / T)

K HOAc = 3.18

1
Giwa Abdulwahab, “Methyl Acetate Reactive Distillation Process Modeling, Simulation and Optimisation Using
Aspen Plus”, (Turkey: ARPN Journal of Engineering and Applied Sciences”, 2013), pp. 1-2
2
Huss Robert, Chen Fengrong et. al., “Reactive distillation for methyl acetate production”, (Massachusetts: Elsevier,
2003), pp. 1-2

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 K MeOH = 4.95

K MeOAc = 0.82

K H20 = 10.5

ai = γi xi

ai is the activity, γi is the liquid activity coefficient, xi is the liquid mole fraction, K1 is the
reaction rate constant (mol/ g cat h), Mcat is the mass of the catalyst (g), and T is the
temperature in K.

The modeling, simulation and optimization of the reactive distillation esterification

reaction was simulated using a RadFrac packed column. The RadFrac packed column is
used to simulate absorption, stripping, extractive distillation, azeotropic distillation with
highly non-ideal liquid solutions and for distillation with on-going chemical reactions.
Since reactive distillation involves simultaneous distillation and reaction steps, the
RadFrac column has been utilized.

The rectification and stripping sections were filled with Raschig type packing of
dimension 25 mm and the reaction section was filled with Sigma type packing material of
10 mm dimension. The packing adds to the surface area of the column and enhances the
number of vapourization/condensation cycles that the feed goes through. This enhances
the efficiency of separation of the lower and higher boiling point components in the feed.
The sensitivity analysis of methyl acetate mole fraction in the distillate and the water
mole fraction in the bottoms product with respect to changes in the molar reflux ratio was
accomplished using the Sensitivity Analysis section of the Model Analysis Tools of
Aspen Plus V 8.4.

3. Conditions for Reactive Distillation Processes

The volatilities of the components must be such that the products can be removed and
reactants retained inside the column. The temperature conditions for both the reaction and
Vapour-Liquid equilibrium must overlap.

Amongst the possible equilibrium column reactive designs, a single-feed column was
used.
The design used in the simulation could be a conceptual starting point for the Eastman
column.
One interpretation of the Eastman column is that simultaneous reaction and separation
occurs in the catalytic section (i.e., below the feed point for the sulfuric acid catalyst)
producing water as a bottom product and the methanol/methyl acetate azeotrope in the
vapor stream leaving the top of this section. This stream then enters a (non-
reactive) extractive section placed on the top of the reactive column, which purifies the
methyl acetate and forces the methanol down into the reaction zone.

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4. Process Modeling
Reactive distillation involves the continuous removal of reaction products. It helps
improve the economic and technical feasibility of processes by helping to improve the
product yield, energy efficiency and reducing capital costs.

In the ASPEN simulation, the production of methyl acetate was simulated using the
following feed conditions:

Table 1: Feed Conditions

Temperature 25 °C
Pressure 101.325 kPa
Feed Flow Rate 2072 kg/h
Composition of Feed (Mole Fraction)
Methanol 0.4
Acetic Acid 0.4
Methyl Acetate 0.1
Water 0.1

Table 2: Reactive Distillation Column Specifications

Number of Trays 15
Top Column Pressure 90 kPa
Bottom Column Pressure 97 kPa
Distillate Rate 20 kgmole/h
Feed Stage 10

For the calculation of Vapour-Liquid equilibria, the Wilson Activity model was used. In
the Methods tab of the Properties page, the Non-Random Two Liquid Property method
was employed.

Figure 1: Main Flow Sheet Design (Single Feed Modification of the Eastman Column)

6
 Figure 2: Setting the Base Method to NRTL for Thermodynamic Calculations

Figure 3: Guidelines for Choosing Thermodynamic Property Methods in ASPEN

7
5. Possible Ranges of Reflux Ratios
At a column pressure of 1 atm, there is a minimum reflux at r = 1.3, and a maximum
reflux at r = 2.8. Outside this range of reflux ratios, even an infinite number of
equilibrium reactive stages will not accomplish the desired separation.
Increasing the pressure increases the minimum number of stages required and reduces the
range of feasible reflux ratios. Designs with a practical number of stages are not possible
at pressures greater than 1 atm, and are not even feasible at pressures greater than 1.3
atm. Thus, for the designing of the reactive distillation column, a pressure of 1 atm has
been assumed.

An increase in temperature leads to a decrease in the equilibrium constant (and hence the
equilibrium conversion) and could potentially trigger unwanted side reactions such as the
dehydration of methanol to dimethylether and water. Thus, the temperature of the
reaction is maintained between 310-325 K.

Figure 4: The optimum reflux ratio would lead to a minimum number of stages.
Also, from the diagram, the feasible range of reflux ratios decreases with
increasing pressure. (Huss Robert, Chen Fengrong .et.al)

6. Simulation Results and Analysis

The sensitivity analysis results reveal that a maximum mole fraction of 40.44 % can be
obtained for a molar reflux ratio of 0.5 in the top product of the reactive distillation
column. The trend was a linear decrease upto a reflux ratio of 1.5 and a flattening out at
40.16% beyond a reflux ratio of 1.5.

8
 For water, the maximum mole fraction in the bottom product was 6.53% at a molar reflux
ratio of 2.5. The mole fraction increased linearly from 5.8% at a reflux ratio of 0.5 to
flatten out at 6.53% beyond a reflux ratio of 1.5.

Figure 5: Sensitivity Analysis of Mole Fraction Methyl Acetate in the Top Product and
Water in the Bottom Product as a Function of Molar Reflux Ratio

7. System Nonlinearity : Input Multiplicity

Reactive distillation columns are highly nonlinear, and thus multiple steady-
state solutions occur.
In this case, input multiplicity is observed, where more than one set of inputs that give the
same outputs.
The fixed outputs are the distillate flow rate and the distillate composition. The feed
inputs are also fixed. The inputs that can vary are the reflux flow rate and the heat input
to the reboiler.
The lightest component (MeOAc) always goes overhead in the distillate, so specifying
the MeOAc mole fraction in the distillate and the distillate flow rate fixes both
conversion and the production rate of the desired product.
Therefore, if we can obtain the same product purity while fixing the distillate flow rate
and varying the reflux ratio, the system will demonstrate input multiplicity.

From figure 4, it is observed that there are two reflux ratios that give the same distillate
flow rate (20 kgmole / h) and the same mole fraction of methyl acetate in the top product.
9
 The more economical design of the two is the one with the lower reflux ratio, as it
involves less energy consumption.

8. Control Structures for Reactive Distillation

A Single Input Single Output (SISO) control structure with PI controllers (P only on
levels) was used for the present control study.
The controllers are tuned using the Tyreus– Luyben tuning method (Tyreus & Luyben,
1992). The relay-feedback method (Yu, 1999) is used to obtain the ultimate gain and
ultimate period. All valves are designed to be half open at steady state. Two first-
order measurement lags with a time constant of 30 s each are used in all composition or
temperature loops.

8.1. Control structure 5

The controlled variables are the temperature in tray 3 and the methanol composition in
tray 11 (Refer to figure 5). The Reflux Ratio is held constant. This control structure is
able to handle changes in disturbance variables well.
With a 20% step increase in the acetic acid flow rate, the system settles in around 4
hours.
Although methyl acetate and water purities are not controlled directly, this structure is
able to indirectly maintain them very close to their set point values. Even with
temperature set- point changes of ±2 K, the methyl acetate mole fraction in the distillate
ranges from 95.98% to 96.03% while water mole fraction in the bottoms ranges from
98.55% to 99.00%.
Figure 6: Control Structure 5 (Al-Arfaj and Luyben 2002)

10
These tests indicate that the CS5 control structure provides effective control. Controlling
an internal composition and one temperature reduces loop interaction and controlling an
intermediate tray temperature significantly reduces the nonlinearity.
This is because the temperature loop follows linear dynamics more closely than does a
composition loop.
There is no direct control of product compositions, so the temperature controller set-point
and the reflux ratio must be set to handle worst-case conditions.

Figure 7: Introduction of a 20% increase in the Disturbance Variable (AcOH) and its
Effects on Different System Variables

11
8.2.Control Structure 7
This inferential control was first suggested by Roat et al. (1986). The two fresh feed flow
rates are manipulated using temperature controllers.
The reflux drum level is controlled by the reflux flow rate, and the base level by the
bottoms flow rate (refer to figure 6).

Figure 8- Control Structure 7 (Al-Arfaj and Luyben 2002)

The distillate flow rate is adjusted to give a constant Reflux Ratio. The heat input to the
reboiler is fixed. The significant advantage of this control structure is that there is no
requirement of composition measurements.

Singular value decomposition is used to select the most sensitive trays to be controlled,
which are Tray 3 and 15. The Niederlinski index for this system is 0.94.
Through closed- loop response tests, it was determined that this control structure handles
load disturbance very effectively.

As shown in Fig. 8 below, a 20% increase in the reboiler heat input (the production
handle) is handled by this structure very well. The temperature controllers increase both
feeds flow rates by the same magnitude which balances the increase in the reboiler heat
input. The methyl acetate and water purities at both ends are maintained close to the
desired levels.

12
Set point changes of ±2 K in the temperature controllers were tested. The results of these
changes show that the structure is not sensitive to inaccuracies in temperature sensors.
Under these temperature set point changes, methyl acetate ranges between 95.9% and
96.1% while water ranges between 98.2% and 99.2%.

Figure 9: Effect of a +20% change in the Reboiler Heat Duty on the Temperature of
Trays 3 and 15, the Feed Flow Rates and the Mole Fraction of Methyl Acetate in the Top
Product and of Water in the Bottoms

13
 Since this structure does not control product purities directly, large disturbances can drive
products off-spec unless the system is designed for purities that are higher than
specifications. More reactive trays, higher tray holdups or catalyst loading are required to
handle the worst-case conditions.

9. Conclusion
The design of a methyl acetate reactive distillation column was modelled using a single-
feed RadFrac column and was based on the Eastman Column specifications.
A simulation of the column and a sensitivity analysis was conducted to determine the
possibility of input multiplicity.
Of the several possible control structures, Control Structures 5 and 7 were identified from
research literature for their control of the process by manipulating tray temperatures.
The CS7 control structure only uses temperature measurements and provides effective
control. The only disadvantage is that the column must not experience extremely large
load variable changes and must be designed for higher than required product purities.

10. Limitations of the Present Study and Future Scope

The simulation was undertaken using alternate design structures. However, with the two
feed reactive distillation column, the feed conditions were not accurately available and so
the simulation could not be carried out with this specified design.
The possibility of several output multiplicities has not been covered as the current project
aims to study the effective control structure that uses tray temperature control to avoid
system nonlinearity only with respect to input multiplicity.
Future work could be carried out to make a comparison between the actual and ideal
methyl acetate systems, and a wider variety of control structures could be evolved to
tackle output multiplicities.

14
11. Appendix

Image 1: Selection of the RadFrac Packed Column in ASPEN Plus

Image 2: Design of the Ideal Eastman Column

Image 3: Main flow Sheet Design Simulated in ASPEN Plus (V 8.4)

15
Image 4: Stream Result Summary After Simulation in ASPEN Plus

16
 12. References:
12.1. “ASPEN Tutorial #6”,
http://courses.washington.edu/overney/Aspen/Aspen_Tutorial_Unit_6.pdf, last accessed
on 20 March, 2015.
12.2. Giwa. A., “Methyl Acetate Reactive Distillation Process Modeling, Simulation
and Optimization Using ASPEN Plus”, ARPN Journal of Engineering and Applied
Sciences: Ankara (2013), Vol. 8, No. 5, pp. 386-392
12.3. Huss, Chen et.al,“Reactive Distillation for Methyl Acetate Production”, Elsevier:
Massachusetts (2003), pp. 1-12
12.4. Al Arfaj, Luyben, “Comparative Control Study of Ideal and Methyl Acetate
Reactive Distillation” , Pergamom: Bethlehem (2002), pp. 1-12
12.5. Bhanu Pratap Singh et.al, “Steady State Analyses for Reactive Distillation
Control: An MTBE Case Study”, Department of Chemical Engineering, Indian Institute
of Technology, Kanpur, pp.1-23

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