To Model Transient Behaviour of a Continuous Stirred Tank Reactor

(Saponification of Ethyl acetate by Sodium hydroxide)

Abdul Nasir Aziz Khan 2002/II M.Sc. Chem 09
April 26, 2008

Overview

Project Objectives Modeling Simulation Model of the Reaction in CSTR Experimental Work Simulation of the model Results and Conclusions

Project Objectives
1.

2.

3.

4.
5.

To get a significant appreciation of the broad use of modeling & simulation techniques in chemical engineering. Develop mathematical model of the reaction for transient and steady state conditions. Develop reaction kinetic data for the saponification of ethyl acetate by sodium hydroxide. Perform simulation of the model. Interpretation of results

MODELING

Modeling

Process Modeling is about knowing and understanding the behaviour of a process and representing it in meaningful ways. The type of representation depends on the end use of this knowledge. These representations are known as Models. Baquette, B. W.: "A process model is a set of equations (including the necessary input data to solve the equations) that allows us to predict the behavior of a chemical process system. "A model (M) for a system (S) and experiment (E) is anything to which (E) can be applied in order to answer questions about (S).

Why do we do modeling?

To understand physical reality of a phenomena and describe it mathematically, To use the mathematically formulated model as a tool to predict the behavior of a system for the new conditions. In order for a model to be used as a simulation tool the model should represent the reality as close as possible. Therefore, validating of a model with a real phenomena is an absolute necessity to gain confidence in a model before using it in a simulation processes.

Modelling in Chemical Engineering

The simple diagram below shows where models can be used for in chemical engineering:
to improve understanding the behavior of the complex systems.

MODELS can be used

in research & development, training & education.

to predict design, control & operation variables.

for simulation, sensitivity analysis, optimization.

to help in experimental design, trouble shooting.

Process Modelling Tools

Modelling Procedure
PHYSICAL PROCESS

SIMULATION TOOL OPTIMIZATION PARAMETER ESTIMATION

SETTING UP THE MODEL FORMULATION

Bad match Good Match

MATHEMATICAL EQUATIONS, BOUNDARY/INITIAL CONDITIONS

VALIDATION & COMPARISON THE RESULTS

NUMERICAL ALGORITHM

COMPUTER SOLUTION

A Generalised Model

Process vs. Process Model

A modeller should have:

a good basic physical and mathematical knowledge, a set of skills & also experience, an intuition, imagination and curiosity.

And the model should

not be more detailed than absolutely necessary! contain as few parameters as possible! have reliable correlations for the parameters!

Model Development
Approaches for Model Development

First-principles modelling

Empirical or, Black box modelling

Semiempirical modelling

First-principles modelling: by writing down the fundamental relationships that describe the process phenomena using the knowledge of physics, chemistry, mathematics, thermodynamics, etc. Empirical or, Black box modelling: collect information by measuring the physical quantities and try to fit an empirical relationship between the quantities of interest. Semiempirical modelling: combination of theoretical and empirical modelling, with one or more parameters to be evaluated from plant data.

Process Modeling Applications

A useful model provides reliable information about a process from the operating conditions of the process. Process models can be used in following areas (in alphabetical order) Equipment maintenance, Fault diagnosis, Planning, Process control, Process design, Process monitoring, Process optimization, and Scheduling. In addition, process models and the development of process models can lead to an overall understanding of the process; i.e., an understanding of the complex interactions within a process.

SIMULATION

Simulation
Process simulation is a computerized model of an actual process. The model is created by inputting into a simulation program all of the critical operating parameters--such as process inputs, process flow and utilized resources--of the real process. With the addition of specific information about how these parameters vary, the resulting model will essentially duplicate the real process.

Rationale
Process simulation successful tool for design,

optimization and control of chemical processes Use of simulation expanded due to availability of high speed computers and software packages Availability of solution techniques further broadened the use of simulation Etc.

Required Competency

Sound understanding of engineering fundamentals (physical system & mechanisms). Process cannot be viewed as a black box! Modeling skills (sound mathematical relations). Computational skills (proper solution technique, software package, computer, etc.)

Impact of Simulation on Chemical Process Industry

Economic: cheaper to use simulation than to build numerous different-size pilot-plants Operation: Easier to develop alternative operating approaches via a mathematical model than by experimental methods Scale up: First-principles simulations can predict system performance in new and different operating conditions

Strategy for simulation of complex chemical processes

Limitations of process simulation...

Lack of data and knowledge of mechanisms Character of computational tools Forgetting assumptions advanced to develop model!

CSTR Model

CSTR

Continuous stirred tank reactors are used commonly in industrial processes. For this type of reactor, mixing is complete, so that the temperature and the composition of the reaction mixture are uniform in all parts of the vessel and are the same as those in the exit stream. Three stages of the continuous operation of a CSTR can be modelled. 1. From beginning to overflow 2. From overflow to steady state 3. Steady state operation The first and second stages are transient and they produce differential equations. The third stage is represented by a steady state model which contains algebraic equations.

Reaction

Dynamics of a CSTR during different stages of its continuous operation is studied by using the saponification of ethyl acetate reaction.

Ethyl acetate+Sodium Hydroxide Sodium acetate+Ethanol

CH3COOC2H5 + NaOH CH3COONa + C2H5OH

The reaction can be considered equimolar and first order with respect to both sodium hydroxide and ethyl acetate i.e. second order overall, within the limits of concentration (0-0.1M) and temperature (20- 40oC) studied.

Stage One

This stage is semibatch. There is no output because the reactor contents do not yet reach the overflow level. A material balance on either NaOH or ethyl acetate (both reactants are at the same concentration and flow rate) gives:
rate of accumulation = rate of input - rate of consumption

Stage One (contd.)

But V is a function of time, and since the system is of constant density and flow rate, a total mass balance gives:

Since at t = 0, V = 0

The above equation is subject to C = Co at t = 0

Stage Two

The second stage is continuous but not yet steady. The concentration is changing with time but the volume of the reactants is constant. A material balance takes the form:
rate of accumulation = rate of input - rate of output - rate of consumption

This may be written as

Where

T=tt is time in minutes and t = V/F is time constant At steady state, C = Cs , which is a particular solution to the above Equation

Stage Three

This is the easiest stage to model, a material balance requires that rate of input = rate of output + rate of consumption

and

Experimental
Work

Equipment

The Conductivity and Concentration Relations

It has been determined that the degree of conversion of the reagents affects the conductivity of the reactor contents so that recording the conductivity with respect to time helps to calculate the amount of conversion with the help of formulas that are provided below.

where A=NaOH, B=EtAc in the reaction: A+B >C+D

The Conductivity and Concentration Relations

The Conductivity and Concentration Relations

.

Specific rate constant

To calculate the specific rate constant k, the overall mass balance may be written as: Rate of change within the reactor = Input Output + Accumulation i.e. for a reactant A in a reactor operating at steady state the volume may be assumed constant and

SIMULATION PROGRAMME

RESULTS

Experimental Vs Calculated Concentration (T=23OC, F=80ml/min, CAo =0.03 moles/litre)

0.03500
Conc. (moles/lit)

0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000

0 140 280 420 560 700 840 980

Experimental Calculated

Tim e (sec)

Experimental Vs Calculated Concentration (T=23OC, F=60ml/min, CAo =0.03 moles/litre)

0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000

Conc. (moles/lit)

Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=23OC, F=80ml/min, CAo =0.04 moles/litre)

0.04500 0.04000 0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000

Conc. (mo les/lit)

Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=23OC, F=60ml/min, CAo =0.04 moles/litre)

0.04500 0.04000 0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000

Conc. (mo les/lit)

Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=30OC, F=80ml/min, CAo =0.03 moles/litre)

0.03500

Conc. (moles/lit)

0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000 Experimental Calculated

140

280

420

560

700

840

Tim e (sec)

980

Experimental Vs Calculated Concentration (T=30OC, F=50ml/min, CAo =0.03 moles/litre)

0.03500

Conc. (mo les/lit)

0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000 Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=30 C, F=80ml/min, CAo =0.04 moles/litre)

0.04500 0.04000 0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000
O

Conc. (mo les/lit)

Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=30 C, F=60ml/min, CAo =0.04 moles/litre)

0.04500 0.04000 0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000
O

Conc. (moles/lit)

Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Experimental Vs Calculated Concentration (T=30OC, F=60ml/min, CAo =0.05 moles/litre)

0.06000

Conc. (mo les/lit)

0.05000 0.04000 0.03000 0.02000 0.01000 0.00000 Experimental Calculated

14 0 28 0 42 0 56 0 70 0 84 0 98 0
Tim e (sec)

Major Conclusions

The graphs show a that the concentration of NaOH obtained by experimental and calculated by the simulation programme are very close to each other. Discrepancies in the experimental and calculated could be caused from slightly unequal concentrations, inadequate mixing, or conductivity calibration problems.

Future Recommendations

The model and simulation can be developed for different feed rates of the reactants. The model and simulation can be developed for a different reaction. The model and simulation can be developed for the PFR and batch reactor also. The model and simulation can be developed for non-isothermal & non-adiabatic conditions.

References
1. Fogler, H. S., Elements of Chemical Reaction Engineering, 2nd edition, Prentice-Hall Inc.,1992. 2. Levenspiel, O., Chemical Reaction Engineering, 2nd edition, John Wiley & Sons, 1971. 3. Smith, J. M., Chemical Engineering Kinetics, 3rd edition, McGraw Hill, 1981. 4. Luyben, W. L., Process Modeling, Simulation and Control for Chemical Engineers, 2nd edition, McGraw Hill, 1990. 5. Ramirez, W. Fred, Computational Methods for Process Simulation, 2nd edition, Butterworth Heinemann,1997.

Questions?